Oxime ester photoinitiators

ABSTRACT

Oxime ester compounds of formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  independently of each other are hydrogen, C 1 -C 20 alkyl, (A), COR 14 , NO 2 , or OR 15 ; provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  is (A), and provided that at least one of the remaining R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  is COR 14  or NO 2 ; R 11  is for example C 1 -C 20 alkyl, M or (B); X and X 1  are for example a direct bond; R 12  and R′ 12  are for example hydrogen or C 1 -C 20 alkyl; R 13  and R′ 13  are for example C 6 -C 20 aryl or C 3 -C 20 heteroaryl; M is (X), (Y) or (Z); X 3  is O, S or NR 19 ; R 14  and R 15  are for example phenyl; R 20 , R 21 , R 22 , R 23 , R 24 , or R 25  for example are hydrogen, COR 14 , NO 2 , or (B); provided that at least two oxime ester groups are present in the molecule; are useful as photoinitiators.

The invention pertains to new oxime ester compounds based on specificcarbazole derivatives and their use as photoinitiators inphotopolymerizable compositions, in particular in photoresistformulations, for example in resins for black matrix in color filterapplications.

Oxime ester compounds having carbazole moieties are known in the art asphotoinitiators. For example EP2015443, WO2008/138724 and EP2141206disclose corresponding compounds. The extremely broad generic scope ofJP 2006-36750-A (corresponding to WO2005/080337) also encompassescompounds with a carbazole moiety and inter alia condensed rings.However, the examples only show ring formation to the carbazole moietyincluding the oxime group. In WO2008/138732 also differentcarbazole-group containing photoinitiator compounds are described. Alsohere the broad generic scope covers a ring formation of substituents atthe carbazole group, while no corresponding examples are disclosed.Further carbazole group containing photoinitiators are disclosed inWO2012/045736.

In photopolymerization technology there still exists a need for highlyreactive, easy to prepare and easy to handle photoinitiators. Forexample, in color filter resist applications, highly pigmented resistsare required for the high color quality property. With the increase ofthe pigment content, the curing of color resists becomes more difficult.Hence, photoinitiators having a high sensitivity are required. Inaddition, also such new photoinitiators must meet the high requirementsof the industry regarding properties like, for example, easy handling,high solubility, thermal stability and storage stability.

Furthermore the initiators in display applications should contribute tosurface smoothness of a pattern, adhesiveness to the substrate etc.

It now has been found, that selected compounds are in particularsuitable as photoinitiators.

Thus, subject of the invention are compounds of the formula I

Compounds of the formula I

wherein

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ independently of each otherare hydrogen, C₁-C₂₀alkyl,

COR₁₄, NO₂, or OR₁₅;

provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, andR₁₀ is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄ or NO₂;

X is CO or a direct bond;

R₁₁ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, orM;

or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈ or M;

or R₁₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₅, NR₁₇R₁₈, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or NR₁₇R₁₈;

R₁₂ is hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy orC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, phenyl, C₁-C₂₀alkylphenyl or CN;

or R₁₂ is phenyl or naphthyl, each of which is unsubstituted orsubstituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl, halogen, CN,OR₁₅, SR₁₆, or NR₁₇R₁₈;

or R₁₂ is C₃-C₂₀heteroaryl, benzyloxy or phenoxy, each of which isunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyland/or halogen;

R₁₃ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl, M, or byC₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O),phenylene, naphthylene or by NR₁₉, or each of which is substituted byone or more C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore halogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl,C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl,OR₁₅, SR₁₆, NR₁₇R₁₈ or by M;

or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore halogen,

OR₁₅, SR₁₆, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, NR₁₇R₁₈, COOR₁₅, CONR₁₇R₁₈,PO(OC_(k)H_(2k+1))₂,

phenyl or by M,

or R₁₃ is C₁-C₂₀alkyl which is substituted by phenyl which issubstituted by one or more halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅,SR₁₆ or by NR₁₇R₁₈;

or R₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene, or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, M, or by phenyl which is substituted byOR₁₅, SR₁₆ or NR₁₇R₁₈;

or R₁₃ is CN, CONR₁₇R₁₈, NO₂, C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl;S(O)_(m)-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl orSO₂—C₁-C₆alkyl;

or R₁₃ is SO₂O-phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl; or is diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl;

M is

k is an integer 1-10;

m is 1 or 2;

R′₁₂ has one of the meanings as given for R₁₂;

R′₁₃ has one of the meanings as given for R₁₃;

R″₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by phenyl orby phenyl which is substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₅, SR₁₆ or by NR₁₇R₁₈;

or R″₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, or by phenyl which is substituted byOR₁₅, SR₁₆ or NR₁₇R₁₈;

or R″₁₃ is CN, CONR₁₇R₁₈, NO₂, C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl;S(O)_(m)-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl orSO₂—C₁-C₆alkyl;

or R″₁₃ is SO₂O-phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl; or is diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl;

or R″₁₃ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR₁₉, or each ofwhich is substituted by one or more C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or by NR₁₇R₁₈;

X₁ is O, CO, S or a direct bond;

X₂ is O, S, SO or SO₂;

X₃ is O, S or NR₁₉;

R₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, or by C₂-C₂₀alkyl which is interrupted by one ormore O, S, or NR₁₉, or each of which is substituted by one or moreC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ orNR₁₇R₁₈;

or R₁₄ is

R₁₅ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OH, SH, CN, C₃-C₆alkenoxy,OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl),C₃-C₂₀cycloalkyl, SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl),O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which is interrupted by oneor more O;

or R₁₅ is C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₁₉,which interrupted C₂-C₂₀alkyl is unsubstituted or substituted byO—C₆-C₂₀arylene-M;

or R₁₅ is (CH₂CH₂O)_(n+1)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl),C₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl or C₃-C₂₀cycloalkyl which isuninterrupted or interrupted by one or more O, S, CO or NR₁₉;

or R₁₅ is C₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted orinterrupted by one or more O;

or R₁₅ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH or C₁-C₃alkoxy;

or R₁₅ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, OH, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino or

n is 1-20;

R₁₆ is hydrogen, C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, or phenyl-C₁-C₃alkyl,wherein the C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, or phenyl-C₁-C₃alkyl isuninterrupted or interrupted by one or more O, S, CO, NR₁₉;

or R₁₆ is C₁-C₂₀alkyl which is unsubstituted or is substituted by one ormore OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl), O(CO)-phenyl or COOR₁₅ orS—C₆-C₂₀arylene-S-M;

or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, S, CO,NR₁₉, which interrupted C₂-C₂₀alkyl is unsubstituted or substituted byS—C₆-C₂₀arylene-M;

or R₁₆ is (CH₂CH₂O)_(n)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₂-C₈alkanoylor C₃-C₆alkenoyl;

or R₁₆ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;

or R₁₆ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, C₁-C₁₂alkyl,C₁-C₄haloalkyl, C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

R₁₇ and R₁₈ independently of each other are hydrogen, C₁-C₂₀alkyl,C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl, C₃-C₂₀cycloalkyl,phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy, C₃-C₁₂alkenoyl,SO₂—(C₁-C₄haloalkyl) or benzoyl;

or R₁₇ and R₁₈ are phenyl, naphthyl or C₃-C₂₀heteroaryl, each of whichis unsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl,C₁-C₂₀alkoxy, C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy;

or R₁₇ and R₁₈ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O, S or NR₁₉, and which 5- or 6-membered saturatedor unsaturated ring is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, ═O, OR₁₅, SR₁₆, NR₂₈R₂₉, COR₃₀, NO₂, halogen,C₁-C₄-haloalkyl, CN, phenyl,

or by C₃-C₂₀cyclalkyl which is uninterrupted or is interrupted by one ormore O, S, CO or NR₁₉;

or R₁₇ and R₁₈ together with the N-atom to which they are attached forma group

R₁₉ is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO, C(O)O, or OC(CO), or isphenyl-C₁-C₄alkyl, C₃-C₈cycloalkyl which is uninterrupted or isinterrupted by one or more O or CO,

or R₁₉ is COR₃₀;

or R₁₉ is phenyl or naphthyl both of which are unsubstituted orsubstituted by one or more C₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₅,SR₁₆, NR₁₇R₁₈, COR₁₄, or

or R₁₉ is C₁-C₆alkylene or C₂-C₆alkenylene linked to the phenyl ornaphthyl ring of the carbazole moiety and forming a 5- or 6-memberedsaturated or unsaturated ring; R₂₀, R₂₁, R₂₂, R₂₃, R₂₄ or R₂₅independently of each other are hydrogen, COR₁₄, NO₂,

or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₄haloalkyl, C₁-C₂₀alkoxy, ═O, OR₁₅, SR₁₆, NR₁₇R₁₈,COR₁₄,

halogen, NO₂, CN, phenyl or by C₃-C₂₀cycloalkyl which is uninterruptedor is interrupted by one or more O, S, CO or NR₁₉;

R₂₆ is COOR₁₅, CONR₁₇R₁₈, (CO)R₁₅; or R₂₆ has one of the meanings givenfor R₁₇ and R₁₈;

R₂₇ is COOR₁₅, CONR₁₇R₁₈, (CO)R₁₅; or R₂₇ has one of the meanings givenfor R₁₅; R₂₈ and R₂₉ independently of each other are hydrogen,C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₃-C₁₀cycloalkyl or phenyl;

or R₂₈ and R₂₉ together with N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring, which is uninterrupted orinterrupted by O, S or NR₁₉, and which 5- or 6-membered saturated orunsaturated ring is not condensed or to which 5- or 6-membered saturatedor unsaturated ring a benzene ring is condensed;

R₃₀ is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO or by NR₁₉, or is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₁₉,

or R₃₀ is phenyl, naphthyl, phenyl-C₁-C₄alkyl, OR₁₅, SR₁₆ or NR₁₇R₁₈;

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently of each otherare hydrogen,

NO₂, COR₁₄, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₁₉;

or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both, R₃₃ and R₃₄ and R₃₅ and R₃₆ are

provided that at least two oxime ester groups selected from the groupconsisting of

are present in the molecule.

The compounds of the formula I are characterized in that they comprisean annelated benzene ring at the carbazole moiety and in that more thanone oxime ester moieties are present in the molecule. Namely thecompound of the formula I comprises more than one, at least two, of thegroups

In addition the compounds of the formula I at least comprise a groupCOR₁₄ or NO₂. Further, via the definition of the radicals R₁₁, R₁₃, R₁₄,namely the group M, the introduction of a further oxime ester bearingaromatic moiety, e.g. a further carbazole group, into the molecule is anoption.

C₁-C₂₀alkyl is linear or branched and is, for example, C₁-C₁₈-, C₁-C₁₄-,C₁-C₁₂-, C₁-C₈-, C₁-C₆- or C₁-C₄alkyl or C₄-C₁₂- or C₄-C₈alkyl. Examplesare methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl,octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,octadecyl and icosyl. C₁-C₆alkyl and C₁-C₁₂alkyl have the same meaningsas given above for C₁-C₂₀alkyl up to the corresponding number ofC-atoms.

C₁-C₄haloalkyl is C₁-C₄alkyl as defined above substituted by halogen asdefined below. The alkyl radical is for example halogenated once, twiceor three times, or mono- or poly-halogenated, up to the exchange of allH-atoms by halogen. It is for example C_(n)H_(x)Hal_(y), whereinx+y=2n+1 and Hal is halogen, preferably F. Specific examples arechloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl,especially trifluoromethyl or trichloromethyl.

C₂-C₄hydroxyalkyl means C₂-C₄alkyl, which substituted by one or more, inparticular one or two OH groups. The alkyl radical is linear orbranched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl,2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl,2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl, or2,4-dihydroxybutyl.

C₂-C₁₀alkoxyalkyl is linear or branched C₂-C₁₀alkyl, which isinterrupted by one O-atom. C₂-C₁₀alkyl has the same meanings as givenabove for C₁-C₂₀alkyl up to the corresponding number of C-atoms.Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.

C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O),phenylene, naphthylene or NR₁₉, is for example interrupted 1-9, 1-5, 1-3or once or twice by O, CO, S, C(O)O, OC(O), phenylene, naphthylene orNR₁₉. If more than one of the defined interrupting radicals are presentthey are of the same kind or different. Two O-atoms are separated by atleast one methylene group, preferably at least two methylene groups,namely ethylene. The alkyl groups are linear or branched. For examplethe following structural units will occur, —CH₂—CH₂—O—CH₂CH₃,—[CH₂CH₂O]_(y)—CH₃, wherein y=1-9, —(CH₂—CH₂O)₇—CH₂CH₃,—CH₂—CH(CH₃)—O—CH₂—CH₂CH₃, —CH₂—CH(CH₃)—O—CH₂—CH₃, —CH₂—CH₂—S—CH₂CH₃,—CH₂—CH(CH₃)—NR₁₉—CH₂—CH₃, —CH₂—CH₂—COO—CH₂CH₃ or—CH₂—CH(CH₃)—OCO—CH₂—CH₂CH₃, —CH₂—CH₂—O(CO)—CH₂CH₃,—CH₂—CH₂—(CO)OCH₂CH₃, —CH₂—CH(CH₃)—O(CO)—CH₂—CH₂CH₃,

etc.

C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkyl and C₃-C₈Cycloalkyl in the context ofthe present application is to be understood as alkyl which at leastcomprises one ring. It is for example cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl andcyclohexyl. C₃-C₁₀cycloalkyl in the context of the present invention isalso meant to cover bicyclic rings, in other words a bridged ring, suchas for example

and corresponding rings. Further examples are structures like

as well as bridged or fused ring systems, e.g.

etc. are also meant to be covered by the term.

C₃-C₂₀cycloalkyl which is interrupted by O, S, CO or NR₁₉ has themeanings given above, wherein at least one CH₂-group of the alkyl isexchanged by either O, S, CO or NR₁₉. Examples are structures like

etc.

C₁-C₈alkyl-C₃-C₁₀cycloalkyl is C₃-C₁₀cycloalkyl as defined above whichis substituted by one or more alkyl groups with up to 8 carbon atoms.Examples are

etc. Further, corresponding interrupted C₁-C₈alkyl-C₃-C₁₀cycloalkylrefers to the C₁-C₈alkyl-C₃-C₁₀cycloalkyl as defined above, where theinterrupting atoms are considered as interrupting either the C₁-C₈alkylor the C₃-C₁₀cycloalkyl, or both.

Examples are

etc.

C₁-C₂₀alkoxy is linear or branched and is C₁-C₂₀alkyl, which issubstituted by one-O-atom, namely C₁-C₂₀alkyl-O—. C₁-C₂₀alkyl has thesame meanings as given above for C₁-C₂₀alkyl up to the correspondingnumber of C-atoms. C₁-C₄alkoxy is linear or branched, for example,methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,isobutyloxy, tert-butyloxy. C₁-C₈alkoxy and C₁-C₄-alkoxy have the samemeanings as described above up to the corresponding numbers of C-atoms.

C₁-C₁₂alkylsulfanyl is linear or branched and is C₁-C₁₂alkyl, which issubstituted by one S-atom, namely C₁-C₁₂alkyl-S—. C₁-C₁₂alkyl has thesame meanings as given above for C₁-C₂₀alkyl up to the correspondingnumber of C-atoms. C₁-C₄alkylsulfanyl is linear or branched, forexample, methylsulfanyl, ethylsulfanyl, propylsulfanyl,isopropylsulfanyl, n-butylsulfanyl, sec-butylsulfanyl, isobutylsulfanyl,tert-butylsulfanyl.

Phenyl-C₁-C₃alkyl or phenyl-C₁-C₄alkyl is for example benzyl,phenylethyl, α-methylbenzyl, α,α-dimethylbenzyl, especially benzyl.

Phenyl-C₁-C₃alkoxyl or phenyl-C₁-C₃alkyloxy is for example benzyloxy,phenylethyloxy, α-methylbenzyloxy or α,α-dimethylbenzyloxy, especiallybenzyloxy.

C₂-C₁₂alkenyl or C₂-C₅alkenyl radicals are linear or branched and aremono- or polyunsaturated and are for example C₂-C₁₀-, C₂-C₈-,C₂-C₅-alkenyl e.g. vinyl, allyl, methallyl, 1,1-dimethylallyl,1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-octenylor dodecenyl, especially allyl. C₂-C₅alkenyl radicals have the samemeanings as given above for C₂-C₁₂alkenyl radicals up to thecorresponding number of C-atoms.

C₂-C₁₂alkenyl which is interrupted by one or more O, S, CO or NR₁₉ isfor example interrupted 1-9, 1-5, 1-3 or once or twice by O, S, CO orNR₁₉. If more than one of the interrupting radicals are present they areof the same kind or different. Two O-atoms are separated by at least onemethylene group, preferably at least two methylene groups, namelyethylene. The alkenyl groups are linear or branched and are defined asabove. For example following structural units can be formed—CH═CH—O—CH₂CH₃, —CH═CH—O—CH═CH₂ etc.

C₃-C₆alkenoxy is mono or polyunsaturated, linear or branched, and hasone of the meanings given for alkenyl above with the attached oxy groupup to the corresponding number of C-atoms. Examples are allyloxy,methallyloxy, butenyloxy, pentenoxy, 1,3-pentadienyloxy, 5-hexenyloxy.

C₁-C₈alkanoyl=C₁-C₈alkylcarbonyl is linear or branched and is, forexample, C₁-C₆- or C₁-C₄alkanoyl or C₄-C₈alkanoyl. Examples are formyl,acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl, hexanoyl, heptanoylor octanoyl, preferably acetyl.

C₃-C₆alkenoyl is mono or polyunsaturated, linear or branched, and is forexample propenoyl, 2-methyl-propenoyl, butenoyl, pentenoyl,1,3-pentadienoyl, 5-hexenoyl.

C₆-C₂₀aryloxycarbonyl is for example phenyloxycabonyl [=phenyl-O—(CO)-],naphtyloxycarbonyl, anthryloxycarbonyl etc.

C₅-C₂₀heteroaryloxycarbonyl is C₅-C₂₀heteroaryl-O—CO—.

C₁-C₂₀alkylphenyl refers to phenyl which is substituted by one or morealkyl groups, where the sum of the C atoms is up to 20.

C₆-C₂₀aryl is for example phenyl, naphthyl, anthryl, phenanthryl,pyrene, chrysene, naphthacene, triphenylene etc., in particular phenylor naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

In the context of the present invention C₃-C₂₀heteroaryl is meant tocomprise either one ring or a multiple ring system, e.g. a fusedring-system. Examples are thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, dibenzofuryl, chromenyl,xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl,pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl,indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl,naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl,carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl,phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl,furazanyl, phenoxazinyl, 7-phenanthryl, anthraquinone-2-yl(=9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl,5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl,4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl,2-phenoxyathiinyl, 2,7-phenoxathiinyl, 2-pyrrolyl, 3-pyrrolyl,5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl,2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl,1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl,1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl,2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl,1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl,1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl,2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl,6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl,6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl,6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl,1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl,6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl,2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl,2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl,7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl,7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl,9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl,1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl,2-acridinyl, 3-acridinyl, 2-perimidinyl, 1-methyl-5-perimidinyl,5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl,3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl,3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl,4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl,10-methyl-2-phenoxazinyl, etc.

C₃-C₂₀heteroaryl in particular is thienyl, benzo[b]thienyl, carbazolyl,thianthrenyl, thioxanthyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl;especially thienyl.

Substituted aryl radicals phenyl, naphthyl, C₆-C₂₀aryl orC₅-C₂₀heteroaryl etc. are substituted 1 to 7, 1 to 6 or 1 to 4 timesrespectively, in particular one, two or three times. It is evident thata defined aryl or heteroaryl radical cannot have more substituents thanfree “CH” or “NH” positions are at the defined ring.

Substituents on the phenyl ring are preferably in positions 4 or in3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration on the phenyl ring.

Interrupted radicals which are interrupted once or more times are forexample interrupted 1-19, 1-15, 1-12, 1-9, 1-7, 1-5, 1-4, 1-3 or once ortwice (it is evident, that the number of interrupting atoms depends onthe number of C-atoms to be interrupted). Substituted radicals, whichare substituted once or more times have for example 1-7, 1-5, 1-4, 1-3or one or two identical or different substituents.

A radical substituted by one or more defined substituents is meant tohave either one substituent or more substituents of identical ordifferent definitions as given. Halogen is fluorine, chlorine, bromineand iodine, especially fluorine, chlorine and bromine, preferablyfluorine and chlorine.

If M is

for example structures like the following are formed

(R₁₁=C₁-C₂₀alkyl substituted by M),

(R₁₁=C₆-C₂₀aryl substituted by M), etc.

If M is

for example structures like the following are formed

(R₁₁=C₁-C₂₀alkyl substituted by M),

R₁₃=C₁-C₂₀alkyl, substituted by M), etc.

If M is

for example structures like the following are formed

(R₁₁=C₆-C₂₀aryl substituted by M), etc.

If R₁₄ is

for example structures like the following are formed

(R₂=COR₁₄), etc.

If R₁₇ and R₁₈ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which optionally isinterrupted by O, S or NR₁₉, saturated or unsaturated rings are formed,for example aziridine, pyrrole, thiazole, pyrrolidine, oxazole,pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine.Preferably, if R₁₇ and R₁₈ together with the N-atom to which they areattached form a 5- or 6-membered saturated or unsaturated ring whichoptionally is interrupted by O, S or NR₁₉, 5- or 6-membered saturatedrings which are not interrupted or which are interrupted by O or NR₁₉,in particular by O, are formed.

If R₂₈ and R₂₉ together with N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring, which is uninterrupted oris interrupted by O, S or NR₁₉, and which 5- or 6-membered saturated orunsaturated ring is not condensed or to which 5- or 6-membered saturatedor unsaturated ring a benzene ring is condensed, saturated orunsaturated rings are formed, for example aziridine, pyrrole, thiazole,pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, piperidine ormorpholine, or corresponding annelated rings, e.g.

etc.

If R₁₉ is C₁-C₆alkylene or C₂-C₆alkenylene linked to the phenyl ornaphthyl ring of the carbazole moiety and forming a 5- or 6-memberedsaturated or unsaturated ring, for example the following structures areformed

(R₁₁=alkyl interrupted by NR₁₉);

(R₁₃=alkyl interrupted by NR₁₉) etc.

If one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted, for examplestructures like the following are formed

etc., in particular

The term “provided that at least two oxime ester groups are present inthe molecule” in any of the claims and the remainder of the text refersto “provided that at least two oxime ester groups selected from thegroup consisting of

are present in the molecule.

The terms “and/or” or “or/and” in the present context are meant toexpress that not only one of the defined alternatives (substituents) maybe present, but also several of the defined alternatives (substituents)together, namely mixtures of different alternatives (substituents).

The term “at least” is meant to define one or more than one, for exampleone or two or three, preferably one or two.

The term “optionally substituted” means, that the radical to which itrefers is either unsubstituted or substituted.

The term “optionally interrupted” means, that the radical to which itrefers is either not interrupted or is interrupted.

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise”, or variations such as“comprises” or “comprising”, will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integers or steps.The term “(meth)acrylate” in the context of the present application ismeant to refer to the acrylate as well as to the correspondingmethacrylate.

The preferences indicated in the text for the compounds according to thepresent invention in the context of this invention are intended to referto all categories of the claims, that is to the claims directed tocompositions, use, process, color filter etc. as well.

R₂ or R₃ for example independently of each other are C₁-C₂₀alkyl,

COR₁₄ or NO₂; and R₁, R₃, R₄, R₅, R₆, R₇, R₈ and R₁₀ are hydrogen.

In particular R₂ is COR₁₄ or NO₂ and R₉ is

R₁, R₃, R₄, R₅, R₆, R₇, R₈ and R₁₀ preferably are hydrogen.

X preferably is a direct bond.

X₁ is for example O, S or a direct bond; or is for example O, CO or adirect bond; or is for example O or a direct bond; or is for example Sor a direct bond; or is for example S or CO; or is for example S and adirect bond; preferably X₁ is a direct bond.

X₂ is for example O, S or SO; or is for example O or S, preferably O.

X₃ is for example O or NR₁₉; or is for example S or NR₁₉; preferablyNR₁₉.

R₁₁ is for example C₁-C₂₀alkyl which is unsubstituted or substituted byone or more halogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈ or M; or isC₂-C₂₀alkyl which is interrupted by one or more O, CO, C(O)O, OC(O)phenylene or NR₁₉, wherein the interrupted C₂-C₂₀alkyl is unsubstitutedor substituted by one or more halogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈,NR₁₇R₁₈ or M; or is phenyl, naphthyl or C₃-C₂₀heteroaryl, in particularthienyl, each of which is unsubstituted or substituted by one or morehalogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, phenyl,C₃-C₈cycloalkyl, OR₁₅, SR₁₆ or NR₁₇R₁₈.

Or R₁₁ is for example C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more halogen, OR₁₅, SR₁₆, NR₁₇R₁₈ or M; or is C₂-C₂₀alkylwhich is interrupted by one or more O, CO, C(O)O, OC(O), phenylene orNR₁₉, wherein the interrupted C₁-C₂₀alkyl is unsubstituted orsubstituted by one or more halogen, OR₁₅, COOR₁₅, NR₁₇R₁₈ or M;

or is phenyl, naphthyl or C₃-C₂₀heteroaryl, in particular thienyl, eachof which is unsubstituted or substituted by one or more halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₅, NR₁₇R₁₈,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl.

Or R₁₁ is for example C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more NR₁₇R₁₈; or is C₂-C₂₀alkyl which is interrupted by one ormore C(O)O, OC(O) or phenylene, wherein the interrupted C₁-C₂₀alkyl isunsubstituted or substituted by NR₁₇R₁₈; or is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular thienyl, each of which is unsubstitutedor substituted by

Preferably R₁₁ is C₁-C₂₀alkyl, phenyl or C₃-C₂₀heteroaryl, in particularthienyl, each of which is unsubstituted or substituted by

R₁₂ is for example hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl,C₁-C₂₀alkoxy, C₁-C₂₀alkyl, phenyl, naphthyl, or C₃-C₂₀heteroaryl.

Or R₁₂ is for example hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl,01-C₂₀alkyl or phenyl.

Or R₁₂ is for example C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkyl, inparticular C₃-C₈cycloalkyl or C₁-C₂₀alkyl, preferably C₁-C₂₀alkyl.

R₁₃ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl, orC₃-C₂₀heteroaryl each of which is unsubstituted or substituted by one ormore phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈, M,or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₁₉, or each of which issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈ or by M; or R₁₃ isC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₅, SR₁₆, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, NR₁₇R₁₈, COOR₁₅,CONR₁₇R₁₈,

phenyl or by M; or

R₁₃ is C₁-C₂₀alkyl which is substituted by phenyl which is substitutedby halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆ or by NR₁₇R₁₈; orR₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or NR₁₉.

Or R₁₃ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl, eachof which is unsubstituted or substituted by one or more OR₁₅, SR₁₆,NR₁₇R₁₈, or each of which is substituted by one or more C₁-C₂₀alkyl; orR₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or moreCOOR₁₅ or by M.

Or R₁₃ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl,preferably phenyl, each of which is unsubstituted or substituted byOR₁₅; or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by oneor more COOR₁₅ or by M.

R′₁₂ has one of the meanings as given for R₁₂; including the examplesand preferences as given above. In particular R′₁₂ is C₁-C₂₀ orC₁-C₄alkyl.

R′₁₃ has one of the meanings as given for R₁₃; including the examplesand preferences as given above. In particular R′₁₃ is C₁-C₂₀alkyl whichis substituted by COOR₁₅, especially C₁-C₄alkyl which is substituted byCOOR₁₅.

R″₁₃ for example is C₁-C₂₀alkyl which is unsubstituted or substituted byphenyl or by phenyl which is substituted by halogen or C₁-C₂₀alkyl; orR″₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene or NR₁₉; or R″₁₃ is CN, CONR₁₇R₁₈, NO₂, C₁-C₄haloalkyl,S(O)_(m)—C₁-C₈alkyl, S(O)_(m)-phenyl; or R″₁₃ is SO₂O-phenyl. C₆-C₂₀arylwhich is unsubstituted or substituted by one or more phenyl, halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂,SO—C₁-C₁₀alkyl, SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interruptedby one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or byNR₁₉, or each of which is substituted by one or more C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, COOR₁₅,CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or byNR₁₇R₁₈.

Or R″₁₃ for example is C₁-C₂₀alkyl which is unsubstituted or substitutedby phenyl; or R″₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O,CO, S, C(O)O, OC(O), phenylene or NR₁₉; R″₁₃ is C₆-C₂₀aryl, inparticular phenyl or naphthyl, each of which is unsubstituted orsubstituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈, or each of which issubstituted by one or more C₁-C₂₀alkyl;

In particular R″₁₃ is C₁-C₂₀alkyl which is unsubstituted or substitutedby phenyl; preferably R″₁₃ is C₁-C₂₀alkyl.

M is for example

in particular a group (X), or (Z);

R₁₄ for example is C₆-C₂₀aryl, in particular phenyl or naphthyl, orC₃-C₂₀heteroaryl each of which is unsubstituted or substituted by one ormore phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈,C₁-C₂₀alkyl or by C₁-C₂₀alkyl which is interrupted by one or more O, S,or NR₁₉; or R₁₄ is

Or R₁₄ for example is C₆-C₂₀aryl, in particular phenyl or naphthyl, eachof which is unsubstituted or substituted by one or more OR₁₅, SR₁₆,NR₁₇R₁₈ or by C₁-C₂₀alkyl; or R₁₄

is

In particular R₁₄ is C₆-C₂₀aryl, in particular phenyl, which isunsubstituted or substituted, in particular substituted, by one or moreOR₁₅, NR₁₇R₁₈ or by C₁-C₂₀alkyl; or R₁₄ is

R₁₅ for example is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, OH, SH, CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(OC)(C₁-C₄alkyl), O(CO)-phenyl, (CO)OH,(CO)O(C₁-C₄alkyl), C₃-C₂₀cycloalkyl, O(C₁-C₂₀arylene)-M, or byC₃-C₂₀cycloalkyl which is interrupted by one or more O; or R₁₅ isC₂-C₂₀alkyl which is interrupted by one or more O, S or NR₁₉; or R₁₅ isC₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl or C₃-C₂₀cycloalkyl; or R₁₅is C₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted or interrupted byone or more O; or R₁₅ is benzoyl; or R₁₅ is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which is unsubstitutedor substituted by one or more halogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy,CN, NO₂, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂,diphenylamino or

Or R₁₅ for example is phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, OH, SH, CN,C₃-C₂₀cycloalkyl, O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which isinterrupted by one or more O; or R₁₅ is C₂-C₂₀alkyl which is interruptedby one or more O, S or NR₁₉; or R₁₅ is phenyl or naphthyl, in particularphenyl, each of which is unsubstituted or substituted by one or morehalogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, CN, NO₂, N(C₁-C₁₂alkyl)₂,diphenylamino or

In particular R₁₅ is C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more halogen or O(C₁-C₂₀arylene)-M.

R₁₆ for example is C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkyl orC₁-C₂₀alkyl; or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or moreO, S, CO, NR₁₉ or COOR₁₅; or R₁₆ is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which is unsubstitutedor substituted by one or more halogen, C₁-C₁₂alkyl, C₁-C₄haloalkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CP)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

Or R₁₆ for example is C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkylor C₁-C₂₀alkyl; or R₁₆ is C₂-C₂₀alkyl which is interrupted by one ormore O, S, CO, NR₁₉ or COOR₁₅; or R₁₆ is phenyl or naphthyl, inparticular phenyl, each of which is unsubstituted or substituted by oneor more halogen, C₁-C₁₂alkyl or

In particular R₁₆ is phenyl which is unsubstituted or substituted, inparticular substituted, by

R₁₇ and R₁₈ for example are independently of each other are hydrogen,C₁-C₂₀alkyl, C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl,C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy,C₃-C₁₂alkenoyl or benzoyl; or R₁₇ and R₁₈ are phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which is unsubstitutedor substituted by one or more halogen, C₁-C₄haloalkyl, C₁-C₂₀alkoxy,C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy; or R₁₇ and R₁₈ together with theN-atom to which they are attached form a 5- or 6-membered saturated orunsaturated ring which is uninterrupted or is interrupted by O or NR₁₉;or R₁₇ and R₁₈ together with the N-atom to which they are attached forma group

Or R₁₇ and R₁₈ for example are independently of each other are hydrogen,C₁-C₂₀alkyl or C₂-C₄hydroxyalkyl; or are phenyl which is unsubstitutedor substituted by one or more halogen or C₁-C₁₂alkyl; or R₁₇ and R₁₈together with the N-atom to which they are attached form a morpholinoring; or R₁₇ and R₁₈ together with the N-atom to which they are attachedform a group

In particular R₁₇ and R₁₈ together with the N-atom to which they areattached form a group

R₁₉ for example is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkylwhich is interrupted by one or more O, CO, C(O)O, or OC(CO), or isphenyl-C₁-C₄alkyl, C₃-C₈cycloalkyl, (CO)R₃₀; or R₁₉ is phenyl ornaphthyl both of which are unsubstituted or substituted by one or moreC₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, COR₁₄, or

or R₁₉ is C₁-C₆alkylene or C₂-C₆alkenylene linked to the phenyl ornaphthyl ring of the carbazole moiety and forming a 5- or 6-memberedsaturated or unsaturated ring.

Or R₁₉ for example is C₁-C₂₀alkyl, C₁-C₄haloalkyl, phenyl-C₁-C₄alkyl,C₃-C₈cycloalkyl or phenyl which is unsubstituted or substituted by oneor more C₁-C₂₀alkyl.

In particular R₁₉ is C₁-C₂₀alkyl.

R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ for example independently of each otherare hydrogen; or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system.

Or R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ for example independently of eachother are hydrogen, or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system.

In particular R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ for example independentlyof each other are hydrogen, or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or R₂₀ and R₂₃ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system.

R₂₈ and R₂₉ for example independently of each other are C₁-C₂₀alkyl; orR₂₈ and R₂₉ together with N-atom to which they are attached form amorpholino ring.

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ for example independently ofeach other are hydrogen,

NO₂, COR₁₄, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, halogen,CN, phenyl or C₃-C₂₀cycloalkyl; or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both,R₃₃ and R₃₄ and R₃₅ and R₃₆ are

Or R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ for example independentlyof each other are hydrogen,

NO₂ or COR₁₄; or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both, R₃₃ and R₃₄ and R₃₅and R₃₆ are

Or R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ for example independentlyof each other are hydrogen,

NO₂ or COR₁₄; or R₃₃ and R₃₄ or R₃₅ and R₃₆ are

Or for example R₃₁, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ for exampleindependently of each other are hydrogen or

and R₃₂ is NO₂ or COR₁₄; or R₃₃ and R₃₄ or R₃₅ and R₃₆ are

In particular R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ for exampleindependently of each other are hydrogen or

Preferably In particular R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₈ arehydrogen and R₃₇ is

Oxime esters of formula I are prepared by methods described in theliterature, for example by reaction of the corresponding oximes with anacyl halide, in particular a chloride, or an anhydride in an inertsolvent such as for example t-butyl methyl ether, tetrahydrofurane (THF)or dimethylformamide in the presence of a base, for exampletriethylamine or pyridine, or in a basic solvent such as pyridine. Asexample in the following the preparation of compounds of the formula I,wherein R₂ is the oxime ester group and X is a direct bond is described:

R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁ and R₁₂ are as defined above,Hal means a halogen atom, in particular Cl.

R₁₂ preferably is methyl.

Such reactions are well known to those skilled in the art, and aregenerally carried out at temperatures of −15 to +50° C., preferably 0 to25° C.

When X is CO, the corresponding oxime is synthesized by the nitrosationof the methylene group with an alkyl nitrite such as for example methylnitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamylnitrite. Then, the esterification is carried out under the samecondition as mentioned above:

Subject of the invention therefore also is a process for the preparationof a compound of the formula I as defined above by reacting thecorresponding oxime compound with an acyl halide of the formula II or ananhydride of the formula III

-   -   wherein Hal is a halogen, in particular Cl, and R₁₂ is as        defined above, in the presence of a base or a mixture of bases.

The oximes required as starting materials can be obtained by a varietyof methods described in standard chemistry textbooks (for instance in J.March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience,1992), or in specialized monographs, for example, S.R. Sandler & W.Karo, Organic functional group preparations, Vol. 3, Academic Press.

One of the most convenient methods is, for example, the reaction ofaldehydes or ketones with hydroxylamine or its salt in polar solventslike dimethylacetamide (DMA), aqueous DMA, ethanol or aqueous ethanol.In that case, a base such as sodium acetate or pyridine is added tocontrol the pH of the reaction mixture. It is well known that the rateof the reaction is pH-dependent, and the base can be added at thebeginning or continuously during the reaction. Basic solvents such aspyridine can also be used as base and/or solvent or cosolvent. Thereaction temperature is generally from room temperature to the refluxingtemperature of the mixture, usually about 20-120° C.

The corresponding ketone intermediates are for example prepared by themethods described in the literature, for example in standard chemistrytextbooks (for instance in J. March, Advanced Organic Chemistry, 4thEdition, Wiley Interscience, 1992). In addition, successiveFriedel-Crafts reaction is effective for synthesis of the intermediates.Such reactions are well known to those skilled in the art.

Another convenient synthesis of oximes is the nitrosation of “active”methylene groups with nitrous acid or an alkyl nitrite. Both alkalineconditions, as described for example in Organic Syntheses coll. Vol. VI(J. Wiley & Sons, New York, 1988), pp 199 and 840, and acidicconditions, as described, for example, in Organic Synthesis coll. vol V,pp 32 and 373, coll. vol. III, pp 191 and 513, coll. vol. II, pp. 202,204 and 363, are suitable for the preparation of the oximes used asstarting materials in the invention. Nitrous acid is usually generatedfrom sodium nitrite. The alkyl nitrite can be for example methylnitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamylnitrite.

Another embodiment of the invention are the free oxime compounds of theformula (IA)

wherein

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are as defined above,provided that at least one group

is replaced by a group

The preferences for the radicals defined for the compounds of theformula (IA) correspond to the ones as given for the compounds of theformula (I) as given in the remaining context of the description, exceptthat defined oxime ester groups are exchanged by the corresponding freeoxime radical.

Every oxime ester group can exist in two configurations, (Z) or (E). Itis possible to separate the isomers by conventional methods, but it isalso possible to use the isomeric mixture as such as photoinitiatingspecies. Therefore, the invention also relates to mixtures ofconfigurational isomers of compounds of the formula I.

Interesting are compounds of the formula I, wherein

R₉ is

R₂ is COR₁₄ and

R₁₄ is

namely compounds of the formula IV:

wherein and R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₁₀, R₁₁, R₁₂, R₂₀, R₂₁, R₂₂,R₂₃, R₂₄, R₂₅ and X₃, are as defined above.

Further interesting are compounds of the formula I, wherein

R₂ is COR₁₄,

R₉ is

R₁₃ is a radical as defined above, substituted by M;

R₁₄ is C₆-C₂₀aryl, which is unsubstituted or substituted as definedabove;

M is

namely compounds of the formula V:

wherein Y is the radical derived from R₁₃, which is substituted by M,

in particular Y is C₆-C₂₀arylene or C₃-C₂₀heteroarylene each of which isunsubstituted or substituted by one or more phenyl, halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₅, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂,SO—C₁-C₁₀alkyl, SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interruptedby one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or byNR₁₉, or each of which is substituted by one or more C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, COOR₁₅,CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆, or byNR₁₇R₁₈;

or Y is C₁-C₂₀alkylene which is unsubstituted or substituted by one ormore halogen, OR₁₅, SR₁₆, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, NR₁₇R₁₈, COOR₁₅,CONR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂,

or by phenyl,

or Y is C₂-C₂₀alkylene which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₂-C₂₀alkylene is unsubstituted or substituted by one or more halogen,OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, or by phenyl which is substituted byOR₁₅, SR₁₆ or NR₁₇R₁₈;

and R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₁₀, R₁₁, R₁₂, R₁₄, R₂₀, R₂₁, R₂₂, R₂₃,R₂₄, R₂₅ and X₃, are as defined above.

Other interesting compounds are compounds of the formula I, wherein R₂is COR₁₄ or

R₉ is

R₁₁ is as defined above, in particular

C₁-C₂₀alkyl which is unsubstituted or substituted by one or more halogenor M;

or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₁-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈ or M;

or R₁₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, M,

namely compounds of the formula VI:

wherein

R₂ is COR₁₄ or

R₁, R₃, R₄, R₅, R₆, R₇, R₈, R₁₀, R₁₁, R₁₂ and R₁₃ are as defined above.

Preferred are Compounds of the formula I as defined above, wherein

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ independently of each otherare hydrogen, C₁-C₂₀alkyl,

or COR₁₄;

provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄;

X is CO or a direct bond;

R₁₁ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, orM;

or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₁-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, or M;

or R₁₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or NR₁₇R₁₈;

R₁₂ is C₁-C₂₀alkyl, phenyl, or C₁-C₈alkoxy;

R₁₃ is phenyl, naphthyl, or C₃-C₂₀heteroaryl each of which isunsubstituted or substituted by one or more phenyl, halogen,C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, M, or by C₂-C₂₀alkyl which isinterrupted by one or more O, CO, S, C(O)O, OC(O), phenylene,naphthylene or by NR₁₉, or each of which is substituted by one or moreC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₄-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₄-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆, NR₁₇R₁₈or by M;

or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore halogen, OR₁₅, SR₁₆, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, NR₁₇R₁₈, COOR₁₅,CONR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, phenyl or by M,

or R₁₃ is C₁-C₂₀alkyl which is substituted by phenyl which issubstituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆ or byNR₁₇R₁₈;

or R₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene, or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, M, or by phenyl which is substituted byOR₁₅, SR₁₆ or NR₁₇R₁₈;

M is

k is an integer 1-10;

m is 1 or 2;

R′₁₂ has one of the meanings as given for R₁₂;

R′₁₃ has one of the meanings as given for R₁₃;

R″₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by phenyl orby phenyl which is substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₅, SR₁₆ or by NR₁₇R₁₈;

or R″₁₃ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, or by phenyl which is substituted byOR₁₅, SR₁₆ or NR₁₇R₁₈;

or R″₁₃ is CN, CONR₁₇R₁₈, NO₂ or C₁-C₄haloalkyl;

R″₁₃ is C₆-C₂₀aryl, in particular phenyl or naphthyl, each of which isunsubstituted or substituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈, or eachof which is substituted by one or more C₁-C₂₀alkyl;

X₁ is O, CO, S or a direct bond;

X₃ is O, S or NR₁₉;

R₁₄ is phenyl, naphthyl, or C₃-C₂₀heteroaryl each of which isunsubstituted or substituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈, M or byC₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, or eachof which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, CONR₁₉R₂₀,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or NR₁₇R₁₈;

or R₁₄ is

R₁₅ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OCH₂CH₂CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl), O(CO)—(C₂-C₄)alkenyl,O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl), C₃-C₂₀cycloalkyl,SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl), O(C₁-C₂₀arylene)-M, or byC₃-C₂₀cycloalkyl which is interrupted by one or more O;

or R₁₅ is C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₁₉;R₁₆ is methyl substituted by COOR₁₅;

or R₁₆ is phenyl unsubstituted or substituted by one or moreC₁-C₁₂alkyl, C₁-C₁₂alkoxy, or

R₁₇ and R₁₈ independently of each other are hydrogen, phenyl,C₁-C₂₀alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy;

or R₁₇ and R₁₈ together with the N-atom to which they are attached forma heteroaromatic ring system which is uninterrupted or is interrupted by

or R₁₇ and R₁₈ together with the N-atom to which they are attached forma group

R₁₉ is hydrogen, C₁-C₂₀alkyl, or C₂-C₂₀alkyl which is interrupted by oneor more O or CO;

or R₁₉ is phenyl or naphthyl both of which are unsubstituted orsubstituted by one or more C₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₅,SR₁₆, NR₁₇R₁₈, COR₁₄, or

R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ independently of each other is hydrogen,COR₁₄, NO₂,

or one of R₂₁ and R₂₂ or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, OR₁₅, SR₁₆, NR₁₇R₁₈, COR₁₄,

NO₂, phenyl;

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently of each otherare hydrogen,

NO₂, COR₁₄, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₁₉;

or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both, R₃₃ and R₃₄ and R₃₅ and R₃₆ are

provided that at least two oxime ester groups are present in themolecule.

Further interesting are Compounds of the formula I as described above,wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ independently of eachother are hydrogen,

or COR₁₄;

provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, andR₁₀ is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄;

X is a direct bond;

R₁₁ is C₁-C₂₀alkyl which is unsubstituted or substituted by NR₁₇R₁₈;

or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more C(O)O, OC(O)or phenylene, wherein the interrupted C₁-C₂₀alkyl is unsubstituted orsubstituted by NR₁₇R₁₈;

or R₁₁ is phenyl or thienyl each of which is unsubstituted orsubstituted by

R₁₂ is C₁-C₂₀alkyl;

R₁₃ is phenyl or thienyl each of which is unsubstituted or substitutedby one or more OR₁₅, SR₁₆, NR₁₇R₁₈, or is substituted by one or moreC₁-C₂₀alkyl;

or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted byC₃-C₈cycloalkyl, COOR₁₅

or by M;

M is

R′₁₂ has one of the meanings as given for R₁₂,

R′₁₃ has one of the meanings as given for R₁₃,

R″₁₃ is C₁-C₂₀alkyl, phenyl or thienyl, wherein the phenyl or thienyl isunsubstituted or substituted by C₁-C₂₀alkyl;

X₁ is a direct bond;

X₂ is O;

X₃ is NR₁₉;

R₁₄ is phenyl or thienyl each of which is unsubstituted or substitutedby one or more OR₁₅, SR₁₆, NR₁₇R₁₈ or C₁-C₂₀alkyl;

or R₁₄ is

R₁₅ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen or O(C₁-C₂₀arylene)-M;

or R₁₅ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is unsubstituted or substituted byO—C₆-C₂₀arylene-M;

R₁₆ is phenyl substituted by

R₁₇ and R₁₈ together with the N-atom to which they are attached form agroup

R₁₉ is C₁-C₂₀alkyl;

R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ independently of each other is hydrogen;or one of R₂₁ and R₂₂ or R₂₄ and R₂₅ is

or R₂₀ and R₂₃ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system;

R₂₆ is COOR₁₅;

R₂₇ is COOR₁₅;

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently of each otherare hydrogen,

NO₂ or COR₁₄;

or R₃₃ and R₃₄ are

provided that at least two oxime ester groups are present in themolecule.

Emphasis has to be laid on compounds of the formula I as defined above,wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ independently of eachother are hydrogen or

COR₁₄,

provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, andR₁₀ is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄;

X is a direct bond;

R₁₁ is C₁-C₂₀alkyl;

or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more C(O)O orOC(O), wherein the interrupted C₂-C₂₀alkyl is substituted by NR₁₇R₁₈;

or is phenyl or thienyl each of which is unsubstituted or substituted by

R₁₂ is C₁-C₂₀alkyl;

R₁₃ is phenyl or thienyl each of which is unsubstituted or substituted,in particular substituted, by OR₁₅, SR₁₆, NR₁₇R₁₈ or C₁-C₂₀alkyl;

or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted byC₃-C₈cycloalkyl, COOR₁₅,

or M;

M is

R′₁₂ has one of the meanings as given for R₁₂; (C₁-C₂₀alkyl which isunsubstituted)

R′₁₃ has one of the meanings as given for R₁₃; (C₁-C₂₀alkyl which issubstituted by COOR₁₅) R″₁₃ is C₁-C₂₀alkyl;

or R″₁₃ is phenyl or thienyl each of which is unsubstituted orsubstituted by C₁-C₂₀alkyl;

X₁ is a direct bond;

X₂ is O;

X₃ is NR₁₉;

R₁₄ is phenyl or thienyl each of which is unsubstituted or substitutedby OR₁₅, SR₁₆, NR₁₇R₁₈ or C₁-C₂₀alkyl;

or R₁₄ is

R₁₅ is C₁-C₂₀alkyl which is unsubstituted or substituted by halogen orO(C₁-C₂₀arylene)-M;

or R₁₅ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is unsubstituted or substituted byO—C₆-C₂₀arylene-M;

R₁₆ is phenyl which is substituted by

R₁₇ and R₁₈ together with the N-atom to which they are attached form agroup

R₁₉ is C₁-C₂₀alkyl;

R₂₀, R₂₁, R₂₂, R₂₃, R₂₄ or R₂₅ independently of each other are hydrogen;

or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or R₂₀ and R₂₃ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system;

R₂₆ is COOR₁₅;

R₂₇ is COOR₁₅;

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently of each otherare hydrogen,

or COR₁₄;

or R₃₃ and R₃₄ are

provided that at least two oxime ester groups selected from the groupconsisting of

are present in the molecule.

The compounds of the formula I are suitable as radical photoinitiators.

Accordingly, subject of the invention is the use of a compound of theformula (I) as defined above for the photopolymerization of acomposition comprising at least one ethylenically unsaturatedphotopolymerizable compound.

Another subject of the present invention therefore is aphotopolymerizable composition comprising

(a) at least one ethylenically unsaturated photopolymerizable compoundand

(b) as photoinitiator, at least one compound of the formula I as definedabove.

The composition may comprise additionally to the photoinitiator (b) atleast one further photoinitiator (c), and/or other additives (d).

The composition may comprise additionally to the photoinitiator (b) atleast one further photoinitiator (c) or other additives (d) or both, atleast one further photoinitiator (c) and other additives (d).

The unsaturated compounds (a) may include one or more olefinic doublebonds. They may be of low (monomeric) or high (oligomeric) molecularmass. Examples of monomers containing a double bond are alkyl,hydroxyalkyl, cycloalkyl (which optionally interrupted by O) or aminoacrylates, or alkyl, hydroxyalkyl, cycloalkyl (which optionallyinterrupted by O) or amino methacrylates, for example methyl, ethyl,butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, tetrahydrofurfurylacrylate, isobornyl acrylate, methyl methacrylate, cyclohexylmethacrylate or ethyl methacrylate. Silicone acrylates are alsoadvantageous. Other examples are acrylonitrile, acrylamide,methacrylamide, N-substituted (meth)acrylamides, vinyl esters such asvinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene,alkyl- and halostyrenes, N-vinylpyrrolidone, vinyl chloride orvinylidene chloride.

Examples of monomers containing two or more double bonds are thediacrylates of ethylene glycol, propylene glycol, neopentyl glycol,hexamethylene glycol or of bisphenol A, and4,4′-bis(2-acryl-oyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate or tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanurate or tris(2-acryloylethyl) isocyanurate.

Examples of polyunsaturated compounds of relatively high molecular mass(oligomers) are acrylated epoxy resins, polyesters containing acrylate-,vinyl ether- or epoxy-groups, and also polyurethanes and polyethers.Further examples of unsaturated oligomers are unsaturated polyesterresins, which are usually prepared from maleic acid, phthalic acid andone or more diols and have molecular weights of from about 500 to 3000.In addition it is also possible to employ vinyl ether monomers andoligomers, and also maleate-terminated oligomers with polyester,polyurethane, polyether, polyvinyl ether and epoxy main chains. Ofparticular suitability are combinations of oligomers which carry vinylether groups and of polymers as described in WO 90/01512. However,copolymers of vinyl ether and maleic acid-functionalized monomers arealso suitable. Unsaturated oligomers of this kind can also be referredto as prepolymers.

Particularly suitable examples are esters of ethylenically unsaturatedcarboxylic acids and polyols or polyepoxides, and polymers havingethylenically unsaturated groups in the chain or in side groups, forexample unsaturated polyesters, polyamides and polyurethanes andcopolymers thereof, polymers and copolymers containing (meth)acrylicgroups in side chains, and also mixtures of one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fattyacids such as linolenic acid or oleic acid. Acrylic and methacrylic acidare preferred.

Suitable polyols are aromatic and, in particular, aliphatic andcycloaliphatic polyols. Examples of aromatic polyols are hydroquinone,4,4′-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and alsonovolaks and resols. Examples of polyepoxides are those based on theabovementioned polyols, especially the aromatic polyols, andepichlorohydrin. Other suitable polyols are polymers and copolymerscontaining hydroxyl groups in the polymer chain or in side groups,examples being polyvinyl alcohol and copolymers thereof orpolyhydroxyalkyl methacrylates or copolymers thereof. Further polyolswhich are suitable are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol,octanediol, dodecanediol, diethylene glycol, triethylene glcyol,polyethylene glycols having molecular weights of preferably from 200 to1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may be partially or completely esterified with onecarboxylic acid or with different unsaturated carboxylic acids, and inpartial esters the free hydroxyl groups may be modified, for exampleetherified or esterified with other carboxylic acids. Examples of estersare:

trimethylolpropane triacrylate, trimethylolethane triacrylate,trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate,tetraethylene glycol diacrylate, pentaerythritol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol diacrylate, dipentaerythritol triacrylate,dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate,pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,tripentaerythritol octamethacrylate, pentaerythritol diitaconate,dipentaerythritol tris-itaconate, dipentaerythritol pentaitaconate,dipentaerythritol hexaitaconate, ethylene glycol diacrylate,1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldiitaconate, sorbitol triacrylate, sorbitol tetraacrylate,pentaerythritol-modified triacrylate, sorbitol tetra methacrylate,sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates andmethacrylates, glycerol diacrylate and triacrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycolwith a molecular weight of from 200 to 1500, or mixtures thereof.

Also suitable as components (a) are the amides of identical ordifferent, unsaturated carboxylic acids with aromatic, cycloaliphaticand aliphatic polyamines having preferably 2 to 6, especially 2 to 4,amino groups. Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- ordi(β-aminopropoxy)ethane. Other suitable polyamines are polymers andco-polymers, preferably with additional amino groups in the side chain,and oligoamides having amino end groups. Examples of such unsaturatedamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide,diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane,β-methacrylamidoethyl methacrylate andN[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and from diols or diamines. Some of the maleic acid canbe replaced by other dicarboxylic acids. They can be used together withethylenically unsaturated comonomers, for example styrene. Thepolyesters and polyamides may also be derived from dicarboxylic acidsand from ethylenically unsaturated diols or diamines, especially fromthose with relatively long chains of, for example 6 to 20 C atoms.Examples of polyurethanes are those composed of saturated or unsaturateddiisocyanates and of unsaturated or, respectively, saturated diols.

Polymers with (meth)acrylate groups in the side chain are likewiseknown. They may, for example, be reaction products of epoxy resins basedon novolaks with (meth)acrylic acid, or may be homo- or copolymers ofvinyl alcohol or hydroxyalkyl derivatives thereof which are esterifiedwith (meth)acrylic acid, or may be homo- and copolymers of(meth)acrylates which are esterified with hydroxyalkyl(meth)acrylates.

Other suitable polymers with acrylate or methacrylate groups in the sidechains are, for example, solvent soluble or alkaline soluble polyimideprecursors, for example poly(amic acid ester) compounds, having thephotopolymerizable side groups either attached to the backbone or to theester groups in the molecule, i.e. according to EP 624826. Sucholigomers or polymers can be formulated with the new photoinitiators andoptionally reactive diluents, like polyfunctional (meth)acrylates inorder to prepare highly sensitive polyimide precursor resists.

The photopolymerizable compounds can be used alone or in any desiredmixtures. It is preferred to use mixtures of polyol (meth)acrylates.

Examples of the component (a) are also polymers or oligomers having atleast two ethylenically unsaturated groups and at least one carboxylfunction within the molecule structure, such as a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy compound and an unsaturatedmonocarboxylic acid, for example, photosensitive compounds as describedin JP 6-1638 and JP 10301276 and commercial products such as EB9696, UCBChemicals; KAYARAD TCR1025, Nippon Kayaku Co., LTD., or an additionproduct formed between a carboxyl group-containing resin and anunsaturated compound having an α,β-unsaturated double bond and an epoxygroup (for example, ACA200M, Daicel Industries, Ltd.).

As diluent, a mono- or multi-functional ethylenically unsaturatedcompound, or mixtures of several of said compounds, can be included inthe above composition up to 70% by weight based on the solid portion ofthe composition.

Subject of the invention also is a photopolymerizable composition asdescribed above, wherein the component (a) is a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy resin and an unsaturatedmonocarboxylic acid.

Such components are for example described in JP06-1938, JP08-278629,JP08-278630, JP10-301276, JP2001-40022, JP10-221843, JP11-231523,JP2002-206014-A or JP2006-53569-A, the disclosure of which hereby isincorporated by reference.

The unsaturated compounds (a) can also be used as a mixture withnon-photopolymerizable, film-forming components. These may, for example,be physically drying polymers or solutions thereof in organic solvents,for instance nitrocellulose or cellulose acetobutyrate. They may also,however, be chemically and/or thermally curable (heat-curable) resins,examples being polyisocyanates, polyepoxides and melamine resins, aswell as polyimide precursors. The use of heat-curable resins at the sametime is important for use in systems known as hybrid systems, which in afirst stage are photopolymerized and in a second stage are crosslinkedby means of thermal aftertreatment.

The invention also provides compositions comprising as component (a) atleast one ethylenically unsaturated photopolymerizable compound which isemulsified or dissolved in water.

Many variants of such radiation-curable aqueous prepolymer dispersionsare commercially available. A prepolymer dispersion is understood asbeing a dispersion of water and at least one prepolymer dispersedtherein. The concentration of water in these systems is, for example,from 5 to 80% by weight, in particular from 30 to 60% by weight. Theconcentration of the radiation-curable prepolymer or prepolymer mixtureis, for example, from 95 to 20% by weight, in particular from 70 to 40%by weight. In these compositions the sum of the percentages given forwater and prepolymer is in each case 100, with auxiliaries and additivesbeing added in varying quantities depending on the intended use.

The radiation-curable, film-forming prepolymers which are dispersed inwater and are often also dissolved are aqueous prepolymer dispersions ofmono- or polyfunctional, ethylenically unsaturated prepolymers which areknown per se, can be initiated by free radicals and have for example acontent of from 0.01 to 1.0 mol of polymerizable double bonds per 100 gof prepolymer and an average molecular weight of, for example, at least400, in particular from 500 to 10′000. Prepolymers with higher molecularweights, however, may also be considered depending on the intendedapplication. Use is made, for example, of polyesters containingpolymerizable C—C double bonds and having an acid number of not morethan 10, of polyethers containing polymerizable C—C double bonds, ofhydroxyl-containing reaction products of a polyepoxide, containing atleast two epoxide groups per molecule, with at least oneα,β-ethylenically unsaturated carboxylic acid, ofpolyurethane(meth)acrylates and of acrylic copolymers which containα,β-ethylenically unsaturated acrylic radicals, as are described in EP12339. Mixtures of these prepolymers can likewise be used. Also suitableare the polymerizable prepolymers described in EP 33896, which arethioether adducts of polymerizable prepolymers having an averagemolecular weight of at least 600, a carboxyl group content of from 0.2to 15% and a content of from 0.01 to 0.8 mol of polymerizable C—C doublebonds per 100 g of prepolymer. Other suitable aqueous dispersions, basedon specific alkyl(meth)acrylate polymers, are described in EP 41125, andsuitable waterdispersible, radiation-curable prepolymers of urethaneacrylates can be found in DE 2936039. Further additives which may beincluded in these radiation-curable aqueous prepolymer dispersions aredispersion auxiliaries, emulsifiers, antioxidants, e.g.2,2-thiobis(4-methyl-6t-butylphenol) or 2,6-di-t-butylphenol, lightstabilizers, dyes, pigments, fillers, such as glass or alumina, forexample talc, gypsum, silicic acid, rutile, carbon black, zinc oxide,iron oxides, reaction accelerators, levelling agents, lubricants,wetting agents, thickeners, flatting agents, antifoams and otherauxiliaries customary in paint technology. Suitable dispersionauxiliaries are water-soluble organic compounds which are of highmolecular mass and contain polar groups, examples being polyvinylalcohols, polyvinylpyrrolidone or cellulose ethers. Emulsifiers whichcan be used are nonionic emulsifiers and, if desired, ionic emulsifiersas well.

It is of course also possible to add other known photoinitiators (c),for example mixtures with camphor quinone; benzophenone, benzophenonederivatives, such as for example given below as sensitzers; ketalcompounds, as for example benzildimethylketal (Irgacure® 651);acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenyl ketones or α-hydroxyalkyl phenyl ketones, such as for example2-hydroxy-2-methyl-1-phenyl-propanone (Darocur® 1173),1-hydroxy-cyclohexyl-phenylketone (Irgacure® 184),1-(4-dodecylbenzoyl)-1-hydroxy-1-methyl-ethane,1-(4-isopropylbenzoyl)-1-hydroxy-1-methyl-ethane,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one(Irgacure® 2959);2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one(Irgacure®127);2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-propan-1-one;1-[4-(benzoyl-phenyl-thia)phenyl]-2-methyl-2-(p-tolylsulfonyl)-propane-1-one(Esacure® 1001M); oligomeric α-hydroxyalkyl phenyl ketones e.g.Esacure®ONE, Esacure®KIP 100; dialkoxyacetophenones,α-aminoacetophenones, e.g.(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane (Irgacure® 907),(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (Irgacure® 369),(4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane(Irgacure® 379),(4-(2-hydroxyethyl)aminobenzoyl)-1-benzyl-1-dimethylaminopropane),(3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane;4-aroyl-1,3-dioxolanes, benzoin alkyl ethers, phenylglyoxalic esters andderivatives thereof, e.g. methyl α-oxobenzeneacetate, oxo-phenyl-aceticacid 2-(2-hydroxy-ethoxy)-ethyl ester, dimeric phenylglyoxalic esters,e.g. oxo-phenyl-acetic acid1-methyl-2-[2-(2-oxo-2-phenyl-acetoxy)-propoxy]-ethyl ester (Irgacure®754); other oximeesters, e.g. 1,2-octanedione1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (Irgacure® OXE01), ethanone1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime)(Irgacure® OXE02), 9H-thioxanthene-2-carboxaldehyde9-oxo-2-(O-acetyloxime), peresters, e.g. benzophenone tetracarboxylicperesters as described for example in EP 126541, monoacyl phosphineoxides, e.g. (2,4,6-trimethylbenzoyl)diphenylphosphine oxide(Darocur®TPO), ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester;bisacylphosphine oxides, e.g.bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethylpentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure® 819),bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide,trisacylphosphine oxides, halomethyltriazines, e.g.2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]-triazene,2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazine,2-methyl-4,6-bis-trichloromethyl-[1,3,5]triazine,hexaarylbisimidazole/coinitiators systems, e.g.ortho-chlorohexaphenyl-bisimidazole combined with2-mercaptobenzthiazole, ferrocenium compounds, or titanocenes, e.g.bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrrylphenyl)titanium(Irgacure® 784).

Further, borate compounds can be used as coinitiators. The Darocur® andIrgacure® compounds are available from BASF SE; Esacure is availablefrom Lamberti SPA. Where the novel photoinitiator systems are employedin hybrid systems, use is made, in addition to the novel free-radicalhardeners, of cationic photoinitiators, of peroxide compounds, such asbenzoyl peroxide (other suitable peroxides are described in U.S. Pat.No. 4,950,581 column 19, lines 17-25), of aromatic sulfonium-,phosphonium- or iodonium salts as described for example in U.S. Pat. No.4,950,581, column 18, line 60 to column 19, line 10 orcyclopentadienylarene-iron(II) complex salts, for example(η⁶-iso-propylbenzene)(η⁵-cyclopentadienyl)iron(II) hexafluorophosphate,as well as oxime sulfonic acid esters, as are, for example described inEP780729. Also pyridinium and (iso)quinolinium salts as described e.g.in EP497531 and EP441232 may be used in combination with the newphotoinitiators.

The new photoinitiators, either alone or in mixtures with other knownphotoinitiators and sensitizers, can be used also in the form of adispersion or emulsion in water or aqueous solutions. In case thecompounds are used in emulsions or dispersions conveniently customarydispersants or emulsifiers are added to prepare a stable emulsion ordispersion. Corresponding suitable additives are known to the personskilled in the art.

The photopolymerizable compositions generally comprise 0.05 to 25% byweight, preferably 0.01 to 10% by weight, in particular 0.01 to 5% byweight of the photoinitiator, based on the solid composition. The amountrefers to the sum of all photoinitiators added, if mixtures ofinitiators are employed. Accordingly, the amount either refers to thephotoinitiator (b) or the photoinitiators (b)+(c).

In addition to the photoinitiator the photopolymerizable mixtures mayinclude various additives (d). Examples of these are thermal inhibitors,which are intended to prevent premature polymerization, examples beinghydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol orsterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol In orderto increase the stability on storage in the dark it is possible, forexample, to use copper compounds, such as copper naphthenate, stearateor octoate, phosphorus compounds, for example triphenylphosphine,tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzylphosphite, quaternary ammonium compounds, for exampletetramethylammonium chloride or trimethylbenzylammonium chloride, orhydroxylamine derivatives, for example N-diethylhydroxylamine. Toexclude atmospheric oxygen during the polymerization it is possible toadd paraffin or similar wax-like substances which, being of inadequatesolubility in the polymer, migrate to the surface in the beginning ofpolymerization and form a transparent surface layer which prevents theingress of air. It is also possible to apply an oxygen-impermeable layeron top of the coating, for example poly(vinylalcohol-co-vinylacetate).Light stabilizers which can be added in a small quantity are UVabsorbers, for example those of the hydroxyphenylbenzotriazole,hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine type.These compounds can be used individually or in mixtures, with or withoutsterically hindered amines (HALS). Examples of such UV absorbers andlight stabilisers are disclosed in WO 04/074328, page 12, line 9 to page14, line 23, said disclosure hereby is incorporated by reference.

To accelerate the photopolymerization it is possible to add amines ascomponent (d), for example triethanolamine, N-methyldiethanolamine,ethyl-p-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate,2-ethylhexyl-p-dimethylaminobenzoate,octyl-para-N,N-dimethylaminobenzoate,N-(2-hydroxyethyl)-N-methyl-para-toluidine or Michler's ketone. Theaction of the amines can be intensified by the addition of aromaticketones of the benzophenone type. Examples of amines which can be usedas oxygen scavengers are substituted N,N-dialkylanilines, as aredescribed in EP339841. Other accelerators, coinitiators and autoxidizersare thiols, thioethers, disulfides, phosphonium salts, phosphine oxidesor phosphines, as described, for example, in EP438123, in GB2180358 andin JP Kokai Hei 6-68309.

It is further possible to add chain transfer agents which are customaryin the art to the compositions according to the invention as component(d). Examples are mercaptans, amines and benzothiazol.

Photopolymerization can also be accelerated by adding furtherphotosensitizers or coinitiators (as component (d)) which shift orbroaden the spectral sensitivity. These are, in particular, aromaticcompounds, for example benzophenone and derivatives thereof,thioxanthone and derivatives thereof, anthraquinone and derivativesthereof, coumarin and phenothiazine and derivatives thereof, and also3-(aroylmethylene)thiazolines, rhodanine, camphorquinone, but alsoeosine, rhodamine, erythrosine, xanthene, thioxanthene, acridine, e.g.9-phenylacridine, 1,7-bis(9-acridinyl)heptane,1,5-bis(9-acridinyl)pentane, cyanine and merocyanine dyes. Examples ofsuitable sensitizer compounds (d) are disclosed in WO 06/008251, page36, line 30 to page 38, line 8, the disclosure of which is herebyincorporated by reference.

A photopolymerizable composition, comprising as further additive (d) aphotosensitizer compound selected from the group consisting ofbenzophenone and its derivatives, thioxanthone and its derivatives,anthraquinone and its derivatives, or coumarine and its derivatives ispreferred.

Examples of benzophenone derivatives, thioxanthone derivatives,anthraquinone derivatives and coumarin derivatives are benzophenone,4-phenyl benzophenone, 4-methoxy benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dimethyl benzophenone, 4,4′-dichlorobenzophenone4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-bis(methylethylamino)benzophenone,4,4′-bis(p-isopropylphenoxy)benzophenone, 4-methyl benzophenone,2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)-benzophenone,3,3′-dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate,4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzophenone,1-[4-(4-benzoyl-phenylsulfanyl)-phenyl]-2-methyl-2-(toluene-4-sulfonyl)-propan-1-one,4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride,2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloridemonohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)-benzophenone,4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyl-benzenemethanaminiumchloride; thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone,2,4-diethylthioxanthone, 2,4-dimethylthioxanthone,1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone,3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxyarbnylthioxanthone,3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3chlorothioxanthone,1-ethoxycarbonyl-3-chlorothioxanthone,1-ethoxycarbonyl-3-ethoxythioxanthne,1-ethoxycarbonyl-3-aminothioxanthone,1-ethoxycarbonyl-3-phenylsulfurylthioxanthone,3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone,1,3-dimethyl-2-hydroxy-9 Hthioxanthen-9-one 2-ethylhexylether,1-ethoxycarbonyl-3-(1-methyl-1-morpholinothyl)-thioxanthone,2-methyl-6-dimethoxymethyl-thioxanthone,2-methyl-6-(1,1-dimethxyenzyl)-thioxanthone,2-morpholinomethylthioxanthone, 2-methyl-6-morpholinoethylhioxanthone,N-allylthioxanthone-3,4-dicarboximide,N-octylthioxanthone-3,4-dicarbximide,N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide,1-phenoxythioanhone, 6-ethoxycarbonyl-2methoxythioxanthone,6-ethoxycarbonyl-2-methylthioxanhone, thioxanthone-2-carboxylic acidpolyethyleneglycol ester,2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-1-propanaminiumchloride, couarin 1, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30,Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153,Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337,Coumarin 500, 3-benzoyl coumarin, 3-benzoyl-7-methoxycoumarin,3-benzoyl-5,7-di methoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin,3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro-coumarin,3,3′-carbonyl-bis[5,7-di(propoxy)coumarin],3,3′-carbonyl-bis(7-methoxycoumarin),3,3′-carbonyl-bis(7-diethylamino-coumarin), 3-isobutyroylcoumarin,3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxy-coumarin,3-benzoyl-5,7-dibutoxycoumarin,3-benzoyl-5,7-di(methoxyethoxy)-coumarin,3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin,3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin,5,7-dimethoxy-3-(1-naphthoyl)-coumarin,5,7-diethoxy-3-(1-naphthoyl)-coumarin, 3-benzoylbenzo[f]coumarin,7-diethylamino-3-thienoylcoumarin,3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, 3-(4-cyanobenzoyl)-5,7-dipropoxycoumarin, 7-dimethylamino-3-phenylcoumarin,7-diethylamino-3-phenylcoumarin, the coumarin derivatives disclosed inJP 09-179299-A and JP 09-325209-A, for example7-[{4-chloro-6-(diethylamino)-S-triazine-2-yl}amino]-3-phenylcoumarin,9,10-anthraquinone and anthracene.

The curing process can be assisted by adding photosensitizers, inparticular, in compositions which are pigmented (for example withtitanium dioxide), and also by adding a component which under thermalconditions forms free radicals, for example an azo compound such as2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for instance a hydroperoxideor peroxycarbonate, for example t-butyl hydroperoxide, as described forexample in EP245639. The compositions according to the invention maycomprise as further additive (d) a photoreducable dye, e.g., xanthene-,benzoxanthene-, benzothioxanthene, thiazine-, pyronine-, porphyrine- oracridine dyes, and/or trihalogenmethyl compounds which can be cleaved byirradiation. Similar compositions are for example described in EP445624.

Further additives known in the art may be added as component (d), as forexample flow improvers, adhesion promoters, such asvinyltrimethoxysilane, vinyltriethoxysilanevinyltris(2-methoxyethoxy)silane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropylmethyldimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane and3-mercaptopropyltrimethoxysilane. Surfactants, optical brighteners,pigments, dyes, wetting agents, levelling assistants, dispersants,aggregation preventers, antioxidants or fillers are further examples foradditives (d).

In order to cure thick and pigmented coatings it is appropriate to addglass microspheres or pulverized glass fibres, as described for examplein U.S. Pat. No. 5,013,768. Further suitable components (d) are, asalready mentioned above, surfactants and dispersants and othercomponents, in particular to support the application of pigments orcolorants in the formulation.

It is preferred to apply a surface treatment to the pigments in order tomake the pigment easy to disperse and to stabilize the resultant pigmentdispersion. The surface treatment reagents are, for example,surfactants, polymeric dispersants, general texture improving agents,pigment derivatives and mixtures thereof. It is especially preferredwhen the colorant composition according to the invention comprises atleast one polymeric dispersant and/or at least pigment derivative.

Suitable surfactants include anionic surfactants such as alkylbenzene-or alkylnahthalene-sulfonates, alkylsulfosuccinates or naphthaleneformaldehyde sulfonates; cationic surfactants including, for example,quaternary salts such as benzyl tributyl ammonium chloride; or nonionicor amphoteric surfactants such as polyoxyethylene surfactants and alkyl-or amidopropyl betaines, respectively.

Illustrative examples of the surfactant include polyoxyethylene alkylethers such as polyoxyethylene lauryl ether, polyoxyethylene stearylether and polyoxyethylene oleyl ether; polyoxyethylene alkylphenylethers such as polyoxyethylene octylphenyl ether and polyoxyethylenenonylphenyl ether; polyethylene glycol diesters such as polyethyleneglycol dilaurate and polyethylene glycol distearate; sorbitan fatty acidesters; fatty acid modified polyesters; tertiary amine modifiedpolyurethanes; polyethyleneimines; those available under the trade namesof KP (a product of Shin-Etsu Chemical Co., Ltd), Polyflow (a product ofKYOEISHA CHEMICAL Co., Ltd), F-Top (a product of Tochem Products Co.,Ltd), MEGAFAC (a product of Dainippon Ink & Chemicals, Inc.), Fluorad (aproduct of Sumitomo 3M Ltd), Asahi Guard and Surflon (products of AsahiGlass Co., Ltd); and the like.

These surfactants may be used alone or in admixture of two or more. Thesurfactant is generally used in an amount of 50 parts or less by weight,preferably 0 to 30 parts by weight, based on 100 parts by weight of thecolorant composition.

Polymeric dispersants include high molecular weight polymers withpigment affinic groups. Examples are: statistical co-polymers comprisedfrom, for instance, styrene derivatives, (meth)acrylates and(meth)acrylamides, and such statistical co-polymers modified by postmodification; block co-polymers and/or comb polymers comprised from, forinstance, styrene derivatives, (meth)acrylates and (meth)acrylamides,and such block co-polymers and/or comb polymers modified by postmodification; polyethylenimines, which for instance is crafted withpolyesters; polyamines, which for instance is crafted with polyesters;and many kinds of (modified) polyurethanes. Polymeric dispersants mayalso be employed. Suitable polymeric dispersants are, for example, BYK'sDISPERBYK® 101, 115, 130, 140, 160, 161, 162, 163, 164, 166, 168, 169,170, 171, 180, 182, 2000, 2001, 2009, 2020, 2025, 2050, 2070, 2090,2091, 2095, 2096, 2150, 2163, 2164, BASFs EFKA® 4008, 4009, 4010, 4015,4020, 4046, 4047, 4050, 4055, 4060, 4061, 4080, 4300, 4310, 4320, 4330,4340, 4400, 4401, 4402, 4403, 4406, 4500, 4510, 4520, 4530, 4540, 4550,4560, 4570, 4580, 4585, 4590, 4800, Ajinomoto Fine Techno's AjisperPB®711, 821, 822, 823, 824, 827, 881, Lubrizol's SOLSPERSE® 1320, 13940,17000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500,32550, 32600, 33500, 34750, 36000, 36600, 37500, 38500, 39000, 41000,41090, 44000, 53095, Kawaken Fine Chemicals' Hinoact KF-1300M, T-6000,T-8000, T-8000E, T-9050, Kusumoto Chemicals' Disparlon PW-36, DA-325,DA-375, DA-7301, Kyoheisha Chemical's Flowlen DOPA-15B, DOPA-15BHFS,DOPA-17HF, DOPA-22, DOPA-33, G-600, G-700, G-820, G-900, NC-500,KDG-2400 and combinations thereof.

It is preferred to use EFKA® 4046, 4047, 4060, 4061, 4300, 4310, 4320,4330, 4340, 4585, DISPERBYK® 161, 162, 163, 164, 165, 166, 168, 169,170, 2000, 2001, 2020, 2050, 2090, 2091, 2095, 2096, 2105, 2150, 2163,2164, PB®711, 821, 822, 823, 824, 827, 881, SOLSPERSE® 24000, 31845,32500, 32550, 32600, 33500, 34750, 36000, 36600, 37500, 39000, 41090,44000, 53095, Hinoact T-6000, T-8000E, Disparlon PW-36, DA-7301, andcombinations thereof as dispersant.

Suitable texture improving agents are, for example, fatty acids such asstearic acid or behenic acid, and fatty amines such as laurylamine andstearylamine. In addition, fatty alcohles or ethoxylated fatty alcohlespolyols such as aliphatic 1,2-diols or epoxidized soy bean oil, waxes,resin acids and resin acid salts may be used for this purpose.

Suitable pigment dispersants are, for example, copper phthalocyaninederivatives such as BASF's EFKA® 6745, Lubrizol's SOLSPERSE® 5000,12000, BYK's SYNERGIST 2100 and azo derivatives such as EFKA® 6750,SOLSPERSE® 22000 and SYNERGIST 2105.

The above mentioned dispersants and surfactants for pigments are forexample employed in compositions of the present invention which are usedas resist formulations, in particular in color filter formulations.

Subject of the invention also is a photopolymerizable composition asdescribed above as further additive (d) comprising a dispersant or amixture of dispersants as well as a photopolymerizable composition asdescribed above as further additive (d) comprising a pigment or amixture of pigments or a mixture of one or more pigments with one ormore dyes.

The choice of additive(s) (d) is made depending on the field ofapplication and on properties required for this field. The additivesdescribed above are customary in the art and accordingly are added inamounts which are usual in the respective application.

Binders (e) as well can be added to the novel compositions. This isparticularly expedient when the photopolymerizable compounds are liquidor viscous substances. The quantity of binder may, for example, be2-98%, preferably 5-95% and especially 20-90%, by weight relative to theoverall solids content. The choice of binder is made depending on thefield of application and on properties required for this field, such asthe capacity for development in aqueous and organic solvent systems,adhesion to substrates and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight ofabout 2,000 to 2,000,000, preferably 3,000 to 1,000,000. Examples ofalkali developable binders are acrylic polymer having carboxylic acidfunction as a pendant group, such as conventionally known copolymersobtained by copolymerizing an ethylenic unsaturated carboxylic acid suchas (meth)acrylic acid, 2-carboxyethyl(meth)acrylic acid,2-carboxypropyl(meth)acrylic acid itaconic acid, crotonic acid, maleicacid, fumaric acid and ω-carboxypolycaprolactone mono(meth)acrylate,with one or more monomers selected from esters of (meth)acrylic acid,such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate,butyl(meth)acrylate, benzyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, glycerolmono(meth)acrylate, tricyclo[5.2.1.0^(2,6)]decan-8-yl (meth)acrylate,glycidyl(meth)acrylate, 2-methylglycidyl(meth)acrylate,3,4-epoxybutyl(meth)acrylate, 6,7-epoxyheptyl(meth)acrylate; vinylaromatic compounds, such as styrene, α-methylstyrene, vinyltoluene,p-chlorostyrene, vinyl benzyl glycidyl ether; amide type unsaturatedcompounds, (meth)acrylamide diacetone acrylamide, N-methylolacrylamide,N-butoxymethacrylamide; and polyolefin type compounds, such asbutadiene, isoprene, chloroprene and the like; methacrylonitrile, methylisopropenyl ketone, mono-2-[(meth)acryloyloxy]ethyl succinate,N-phenylmaleimide, maleic anhydride, vinyl acetate, vinyl propionate,vinyl pivalate, polystyrene macromonomer, or polymethyl(meth)acrylatemacromonomer. Examples of copolymers are copolymers of acrylates andmethacrylates with acrylic acid or methacrylic acid and with styrene orsubstituted styrene, phenolic resins, for example novolak,(poly)hydroxystyrene, and copolymers of hydroxystyrene with alkylacrylates, acrylic acid and/or methacrylic acid. Preferable examples ofcopolymers are copolymers of methyl methacrylate/methacrylic acid,co-polymers of benzyl methacrylate/methacrylic acid, copolymers ofmethyl methacrylate/ethyl acrylate/methacrylic acid, copolymers ofbenzyl methacrylate/methacrylic acid/styrene, copolymers of benzylmethacrylate/methacrylic acid/hydroxyethyl methacrylate, copolymers ofmethyl methacrylate/butyl methacrylate/methacrylic acid/styrene,copolymers of methyl methacrylate/benzyl methacrylate/methacrylicacid/hydroxyphenyl methacrylate. Examples of solvent developable binderpolymers are poly(alkyl methacrylates), poly(alkyl acrylates),poly(benzylmethacrylate-co-hydroxyethylmethacrylate-co-methacrylicacid), poly(benzylmethacrylate-co-methacrylic acid); cellulose estersand cellulose ethers, such as cellulose acetate, celluloseacetobutyrate, methylcellulose, ethylcellulose; polyvinylbutyral,polyvinylformal, cyclized rubber, polyethers such as polyethylene oxide,polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate,polyurethane, chlorinated polyolefins, polyvinyl chloride, vinylchloride/vinylidene copolymers, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene/vinyl acetate), polymers such as polycaprolactam andpoly(hexamethylene adipamide), and polyesters such as poly(ethyleneglycol terephtalate) and poly(hexamethylene glycol succinate) andpolyimide binder resins.

The polyimide binder resin in the present invention can either be asolvent soluble polyimide or a polyimide precursor, for example, apoly(amic acid).

Preferred is a photopolymerizable composition, comprising as binderpolymer (e), a copolymer of methacrylate and methacrylic acid.

Interesting further are polymeric binder components as described e.g. inJP 10-171119-A, in particular for use in color filters.

Subject of the invention further is a photopolymerizable composition asdescribed above, wherein the component (a) is a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy resin and an unsaturatedmonocarboxylic acid.

The photopolymerizable compositions can be used for various purposes,for example as printing ink, e.g. screen printing inks, inks for offset-or flexo printing, as a clear, white or colored finish, for example forwood, plastic or metal, as powder coating, as a coating material, interalia for paper, wood, metal or plastic, as a daylight-curable coatingfor the marking of buildings and roadmarking, for photographicreproduction techniques, for holographic recording materials, for imagerecording techniques or to produce printing plates which can bedeveloped with organic solvents or with aqueous alkalis, for producingmasks for screen printing, as dental filling compositions, as adhesives,as pressure-sensitive adhesives, as laminating resins, as etch resists,solder resists, electroplating resists, or permanent resists, bothliquid and dry films, as photostructurable dielectric, for printedcircuit boards and electronic circuits, as resists to manufacture colorfilters for a variety of display applications or to generate structuresin the manufacturing process of plasma-display panels andelectroluminescence displays, (as for example described in U.S. Pat. No.5,853,446, EP863534, JP 09-244230-A, JP10-62980-A, JP08-171863-A, U.S.Pat. No. 5,840,465, EP855731, JP05-271576-A, JP 05-67405-A) for theproduction of holographic data storage (HDS) material, for theproduction of optical switches, optical lattices (interference lattice),light circuits, for producing three-dimensional articles by mass curing(UV curing in transparent moulds) or by the stereolithography technique,as is described, for example, in U.S. Pat. No. 4,575,330, to producecomposite materials (for example styrenic polyesters, which may, ifdesired, contain glass fibres and/or other fibres and other auxiliaries)and other thick-layered compositions, for coating or sealing electroniccomponents and integrated circuits, or as coatings for optical fibres,or for producing optical lenses, e.g. contact lenses or Fresnel lenses.The compositions according to the invention are further suitable for theproduction of medical equipment, auxiliaries or implants. Further, thecompositions according to the invention are suitable for the preparationof gels with thermotropic properties, as for example described inDE19700064 and EP678534.

The novel photoinitiators may additionally be employed as initiators foremulsion polymerizations, pearl polymerizations or suspensionpolymerizations, as polymerization initiators for fixing ordered statesof liquid-crystalline monomers and oligomers, or as initiators forfixing dyes on organic materials.

In coating materials, use is frequently made of mixtures of a prepolymerwith polyunsaturated monomers, which may additionally include amonounsaturated monomer as well. It is the prepolymer here whichprimarily dictates the properties of the coating film, and by varying itthe skilled worker is able to influence the properties of the curedfilm. The polyunsaturated monomer functions as a crosslinking agentwhich renders the film insoluble. The monounsaturated monomer functionsas a reactive diluent, which is used to reduce the viscosity without theneed to employ a solvent.

Unsaturated polyester resins are usually used in two-component systemstogether with a monounsaturated monomer, preferably with styrene. Forphotoresists, specific one-component systems are often used, for examplepolymaleimides, polychalcones or polyimides, as described in DE 2308830.

The novel photoinitiators can also be used for the polymerization ofradiation-curable powder coatings. The powder coatings can be based onsolid resins and monomers containing reactive double bonds, for examplemaleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. Afree-radically UV-curable powder coating can be formulated by mixingunsaturated polyester resins with solid acrylamides (for example methylmethylacrylamidoglycolate) and a novel free-radical photoinitiator, suchformulations being as described, for example, in the paper “RadiationCuring of Powder Coating”, Conference Proceedings, Radtech Europe 1993by M. Wittig and Th. Gohmann. The powder coatings can also containbinders, as are described, for example, in DE 4228514 and in EP 636669.Free-radically UV-curable powder coatings can also be formulated bymixing unsaturated polyester resins with solid acrylates, methacrylatesor vinyl ethers and with a novel photoinitiator (or photoinitiatormixture). The powder coatings may also comprise binders as aredescribed, for example, in DE 4228514 and in EP 636669. The UV-curablepowder coatings may additionally comprise white or coloured pigments.For example, preferably rutiletitanium dioxide can be employed inconcentrations of up to 50% by weight in order to give a cured powdercoating of good hiding power. The procedure normally compriseselectrostatic or tribostatic spraying of the powder onto the substrate,for example metal or wood, melting of the powder by heating, and, aftera smooth film has formed, radiation-curing of the coating withultraviolet and/or visible light, using for example medium-pressuremercury lamps, metal halide lamps or xenon lamps. A particular advantageof the radiation-curable powder coatings over their heat-curablecounterparts is that the flow time after melting the powder particlescan be delayed in order to ensure the formation of a smooth, high-glosscoating. In contrast to heat-curable systems, radiation-curable powdercoatings can be formulated to melt at lower temperatures without theunwanted effect of shortening their lifetime. For this reason, they arealso suitable as coatings for heat-sensitive substrates, for examplewood or plastics. In addition to the novel photoinitiator systems, thepowder coating formulations may also include UV absorbers. Appropriateexamples are listed above in sections 1.-8.

The novel photocurable compositions are suitable, for example, ascoating materials for substrates of all kinds, for example wood,textiles, paper, ceramics, glass, plastics such as polyesters,polyethylene terephthalate, polyolefins or cellulose acetate, especiallyin the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg orCo and GaAs, Si or SiO₂ to which it is intended to apply a protectivelayer or, by means of imagewise exposure, to generate an image.

The novel radiation-sensitive compositions further find application asnegative resists, having a very high sensitivity to light and being ableto be developed in an aqueous alkaline medium without swelling. They aresuitable for the production of printing forms for relief printing,planographic printing, photogravure or of screen printing forms, for theproduction of relief copies, for example for the production of texts inbraille, for the production of stamps, for use in chemical milling or asa microresist in the production of integrated circuits. The compositionsfurther may be used as photopatternable dielectric layer or coating,encapsulating material and isolating coating in the production ofcomputer chips, printed boards and other electric or electroniccomponents. The possible layer supports, and the processing conditionsof the coating substrates, are just as varied.

The novel composition also relates to a photosensitive thermosettingresin composition and a method of forming a solder resist pattern by theuse thereof, and more particularly relates to a novel photosensitivethermosetting resin composition useful as materials for the productionof printed circuit boards, the precision fabrication of metallicarticles, the etching of glass and stone articles, the relief of plasticarticles, and the preparation of printing plates and particularly usefulas a solder resist for printed circuit boards and to a method of forminga solder resist pattern by the steps of exposing a layer of the resincomposition selectively to an actinic ray through a photomask having apattern and developing the unexposed part of the layer.

The solder resist is a substance which is used during the soldering of agiven part to a printed circuit board for the purpose of preventingmolten solder from adhering to irrelevant portions and protectingcircuits. It is, therefore, required to possess such properties as highadhesion, insulation resistance, resistance to soldering temperature,resistance to solvents, resistance to alkalis, resistance to acids, andresistance to plating.

Because the photocurable compositions according to the invention have agood thermal stability and are sufficiently resistant to inhibition byoxygen, they are particularly suitable for the production of colorfilters or color mosaic systems, such as described, for example, in EP320 264. Color filters usually are employed in the manufacturing of flatpanel displays such as LCD's, PDP (plasma panel display), EL(electroluminessence) display, and projection systems, image sensors,CCD (charge coupled device), and CMOS (complementary metal oxidesemiconductor) sensors for scanner, digital camera and video camera.

The color filters usually are prepared by forming red, green and bluepixels and a black matrix on a glass substrate. In these processesphotocurable compositions according to the invention can be employed. Aparticularly preferred method of use comprises adding of the coloringmatters, dyes and pigments of red, green and blue colors to thelight-sensitive resin composition of the present invention, coating ofthe substrate with the composition, drying of the coating with a shortheat treatment, patternwise exposure of the coating to actinic radiationand subsequent development of the pattern in an aqueous alkalinedeveloper solution and optionally a heat treatment. Thus, bysubsequently applying a red, green and blue pigmented coating, in anydesired order, on top of each other with this process a color filterlayer with red, green and blue color pixels can be produced.

The development is carried out by washing out the areas which were notpolymerized with a suitable alkali developing solution. This process isrepeated to form the image having plural colors.

In the light-sensitive resin composition of the present invention, witha process in which at least one or more picture elements are formed on atransparent substrate and then an exposure is given from a side of thetransparent substrate, on which the above picture elements are notformed, the above picture elements can be utilized as a light-shieldingmask. In this case, for example, in the case where an overall exposureis given, a position adjustment of a mask gets unnecessary and a concernon a position slippage thereof is removed. And, it is possible to cureall of the part on which the above picture elements are not formed.Further, in this case, it is possible as well to develop and remove apart of the portion on which the above picture elements are not formedby using partially a light-shielding mask.

Since in either case, no gap is formed between the picture elementswhich are formed formerly and those which are formed later, thecomposition of the present invention is suitable for, for example, aforming material for a color filter. To be concrete, the coloringmatters, dyes and pigments of red, green and blue colors are added tothe light-sensitive resin composition of the present invention, and theprocesses for forming an image are repeated to form the picture elementsof red, green and blue colors. Then, the light-sensitive resincomposition to which, for example, the black coloring materials, dyesand pigments are added is provided on an overall face. An overallexposure (or a partial exposure via a light-shielding mask) can beprovided thereon to form the picture elements of a black color all overthe spaces (or all but a partial region of the light-shielding mask)between the picture elements of red, green and blue colors.

In addition to a process in which the light-sensitive resin compositionis coated on a substrate and dried, the light-sensitive resincomposition of the present invention can be used as well for a layertransfer material. That is, the light-sensitive resin composition islayer-wise provided directly on a temporary support, preferably on apolyethylene terephthalate film, or on a polyethylene terephthalate filmon which an oxygen-shielding layer and a peeling layer or the peelinglayer and the oxygen-shielding layer are provided. Usually, a removablecover sheet made of a synthetic resin is laminated thereon for aprotection in handling. Further, there can be applied as well a layerstructure in which an alkali soluble thermoplastic resin layer and anintermediate layer are provided on a temporary support and further alight-sensitive resin composition layer is provided thereon (JP5-173320-A).

The above cover sheet is removed in use and the light-sensitive resincomposition layer is laminated on a permanent support. Subsequently,peeling is carried out between those layer and a temporary support whenan oxygen-shielding layer and a peeling layer are provided, between thepeeling layer and the oxygen-shielding layer when the peeling layer andthe oxygen-shielding layer are provided, and between the temporarysupport and the light-sensitive resin composition layer when either thepeeling layer or the oxygen-shielding layer is not provided, and thetemporary support is removed.

A metal support, glass, ceramics, and a synthetic resin film can be usedas a support for a color filter. Glass and a synthetic resin film whichis transparent and have an excellent dimension stability is particularlypreferred.

The thickness of the light-sensitive resin composition layer is usually0.1 to 50 micrometers, in particular 0.5 to 5 micrometers.

A diluted aqueous solution of an alkaline substance can be used as adeveloping solution for the light-sensitive resin composition of thepresent invention if the composition contains alkali soluble resin oralkali soluble monomers or oligomers, and further a developer solutionprepared by adding a small amount of a water-miscible organic solventthereto is included as well.

Examples of suitable alkaline materials include alkali metal hydroxides(for example, sodium hydroxide and potassium hydroxide), alkali metalcarbonates (for example, sodium carbonate and potassium carbonate),alkali metal bicarbonates (for example, sodium bicarbonate and potassiumbicarbonate), alkali metal silicates (for example, sodium silicate andpotassium silicate), alkali metal metasilicates (for example, sodiummetasilicate and potassium metasilicate), triethanolamine,diethanolamine, monoethanolamine, morpholine, tetraalkylammoniumhydroxides (for example, tetramethylammonium hydroxide), or trisodiumphosphate. The concetration of the alkaline substance is 0.01 to 30weight %, and pH is preferably 8 to 14.

Suitable organic solvents which are miscible with water includemethanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono-n-butyl ether, diethyleneglycol dimethyl ether,propyleneglycol monomethyl ether acetate, ethyl-3-ethoxypropionate,methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone,methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,2-pentanone, epsilon-caprolactone, gamma-butylolactone,dimethylformamide, dimethylacetoamide, hexamethylphosphoramide, ethyllactate, methyl lactate, epsilon-caprolactam, andN-methyl-pyrrolidinone. The concentration of the organic solvent whichis miscible with water is 0.1 to 30 weight %.

Further, a publicly known surface active agent can be added. Theconcentration of the surface active agent is preferably 0.001 to 10weight %.

The light sensitive resin composition of the present invention can alsobe developed with organic solvents, including blends of two or moresolvents, not containing alkaline compounds. Suitable solvents includemethanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono-n-butyl ether, diethyleneglycol dimethyl ether,propyleneglycol monomethyl ether acetate, ethyl-3-ethoxypropionate,methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone,methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,2-pentanone, epsilon-caprolactone, gamma-butylolactone,dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyllactate, methyl lactate, epsilon-caprolactam, and N-methylpyrrolidinone.Optionally, water can be added to these solvents up to a level at whichstill a clear solution is obtained and at which sufficient solubility ofthe unexposed areas of the light sensitive composition is maintained.

The developer solution can be used in all forms known to the personskilled in the art, for example in form of a bath solution, puddle, or aspraying solution. In order to remove the non-cured portion of thelight-sensitive resin composition layer, there can be combined themethods such as rubbing with a rotary brush and rubbing with a wetsponge. Usually, the temperature of the developing solution ispreferably at and around room temperature to 40° C. The developing timeis changeable according to the specific kind of the light-sensitiveresin composition, the alkalinity and temperature of the developingsolution, and the kind and concentration of the organic solvent in thecase where it is added. Usually, it is 10 seconds to 2 minutes. It ispossible to put a rinsing step after the development processing.

A final heat treatment is preferably carried out after the developmentprocessing. Accordingly, a support having a layer which isphotopolymerized by exposing (hereinafter referred to as a photocuredlayer) is heated in an electric furnace and a drier, or the photocuredlayer is irradiated with an infrared lamp or heated on a hot plate. Theheating temperature and time depend on the composition used and thethickness of the formed layer. In general, heating is preferably appliedat about 120° C. to about 250° C., for about 5 to about 60 minutes.

The pigment which can be comprised in the composition according to thepresent invention, including a pigmented color filter resistcomposition, is preferably a processed pigment, for example a powdery orpasty product prepared by finely dispersing a pigment into at least oneresin selected from the group consisting of acrylic resin, vinylchloride-vinyl acetate copolymer, maleic acid resin and ethyl celluloseresin. The red pigment comprises, for example, an anthraquinone typepigment alone, a diketopyrolopyrole type pigment alone, a mixture ofthem or a mixture consisting of at least one of them and a disazo typeyellow pigment or an isoindoline type yellow pigment, in particular C.I. Pigment Red 177 alone, C. I. Pigment Red 254 alone, a mixture of C.I. Pigment Red 177 and C. I. Pigment Red 254 or a mixture consisting ofat least one member of C. I. Pigment Red 177 and C. I. Pigment Red 254,and C. I. Pigment Yellow 83 or C. I. Pigment Yellow 139 (“CI” refers tothe Color Index, known to the person skilled in the art and publiclyavailable).

Further suitable examples for the pigment are C.I. Pigment Red 9, 97,105, 122, 123, 144, 149, 168, 176, 179, 180, 185, 202, 207, 209, 214,222, 242, 244, 255, 264, 272 and C.I. Pigment Yellow 12, 13, 14, 17, 20,24, 31, 53, 55, 93, 95, 109, 110, 128, 129, 138, 139, 150, 153, 154,155,166, 168, 185, 199, 213 and C.I. Pigment Orange 43. Examples of the dyesfor red color are C. I. Solvent Red 25, 27, 30, 35, 49, 83, 89, 100,122, 138, 149, 150, 160, 179, 218, 230, C. I. Direct Red 20, 37, 39, 44,and C. I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 51, 52, 87, 88, 89, 92,94, 97, 111, 114, 115, 134, 145, 151, 154, 180, 183, 184, 186, 198, C.I. Basic Red 12, 13, C. I. Disperse Red 5, 7, 13, 17 and 58. The Reddyes can be used in combination with yellow and/or orange dyes. Thegreen pigment comprises for instance a halogenated phthalocyanine typepigment alone or its mixture with a disazo type yellow pigment, anquinophthalone type yellow pigment or a metal complex, in particular C.I. Pigment Green 7 alone, C. I. Pigment Green 36 alone, or a mixtureconsisting of at least one member of C. I. Pigment Green 7, C. I.Pigment Green 36 and C. I. Pigment Yellow 83, C. I. Pigment Yellow 138or C. I. Pigment Yellow 150. Other suitable green pigments are C.I.Pigment Green 15, 25 and 37.

Examples for suitable green dyes are C. I. Acid Green 3, 9, 16, C. I.Basic Green 1 and 4.

Examples for suitable blue pigments are phthalocyanine type pigments,used either alone or in combination with an dioxazine type violetpigment, for instance, C. I. Pigment Blue 15:6 alone, a combination ofC. I. Pigment Blue 15:6 and C. I. Pigment Violet 23. Further examplesfor blue pigments are such of C. I. Pigment Blue 15:3, 15:4, 16, 22, 28and 60. Other suitable pigments are C. I. Pigment Violet 14,19, 23, 29,32, 37, 177 and C. I. Orange 73.

Examples for suitable blue dyes are C. I. Solvent Blue 25, 49, 68, 78,94, C. I. Direct Blue 25, 86, 90, 108, C. I. Acid Blue 1, 7, 9, 15, 103,104, 158, 161, C. I. Basic Blue 1, 3, 9, 25, and C. I. Disperse Blue198.

The pigment of the photopolymeric composition for black matrixpreferably comprises at least one member selected from the groupconsisting of carbon black, titanium black and iron oxide. However, amixture of other pigments which, in total, give the black appearance,can also be used. For example, also C. I. Pigment Black 1, 7 and 31 canbe used alone or in combination.

Other examples of the dyes used for color filter are C. I. SolventYellow 2, 5, 14, 15, 16, 19, 21, 33, 56, 62, 77, 83, 93, 162, 104, 105,114, 129, 130, 162, C. I. Disperse Yellow 3, 4, 7, 31, 54, 61, 201, C.I. Direct Yellow 1, 11, 12, 28, C. I. Acid Yellow 1, 3, 11, 17, 23, 38,40, 42, 76, 98, C. I. Basic Yellow 1, C. I. Solvent Violet 13, 33, 45,46, C. I. Disperse Violet 22, 24, 26, 28, C. I. Acid Violet 49, C. I.Basic Violet 2, 7, 10, C. I. Solvent Orange 1, 2, 5, 6, 37, 45, 62, 99,C. I. Acid Orange 1, 7, 8, 10, 20, 24, 28, 33, 56, 74, C. I. DirectOrange 1, C. I. Disperse Orange 5, C. I. Direct Brown 6, 58, 95, 101,173, C. I. Acid Brown 14, C. I. Solvent Black 3, 5, 7, 27, 28, 29, 35,45 and 46.

In some special cases of manufacturing color filters, complementarycolors, yellow, magenta, cyan and optionally green, are used instead ofred, green and blue. As yellow for this type of color filters, theabovementioned yellow pigments and dyes can be employed. Examples of thecolorants suitable for magenta color are C. I. Pigment Red 122, 144,146, 169, 177, C. I. Pigment Violet 19 and 23. Examples of cyan colorare aluminum phthalocyanine pigments, titanium phthalocyanine pigments,cobalt phthalocyanine pigments, and tin phthalocyanine pigments.

For any color, combinations of more than two pigments can also be used.Especially suitable in color filter applications are powdery processedpigments prepared by finely dispersing the above mentioned pigments intoa resin.

The concentration of the pigment in the total solid component (pigmentsof various colors and resin) is for example in the range of 5% to 80% byweight, in particular in the range of 20% to 45% by weight.

The pigments in the color filter resist composition have preferably amean particle diameter smaller than the wavelength of visible light (400nm to 700 nm). Particularly preferred is a mean pigment diameter of <100nm.

If necessary, the pigments may be stabilized in the photosensitivecomposition by pretreatment of the pigments with a dispersant to improvethe dispersion stability of the pigment in the liquid formulation.Suitable additives are described above.

Preferably, the color filter resist composition according to the presentinvention contains additionally at least one addition polymerizablemonomeric compound as component (a).

The ethylenically unsaturated compounds (a), also for the color filterresist applications are as described above

Suitable examples of esters as component (a) based on polyols aretrimethylolpropane tri(meth)acrylate, trimethylolpropanetri(acryloyloxypropyl)ether, trimethylolethane tri(meth)acrylate,ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,triethylene glycol di(meth)acrylate, tetraethylene glycoldi(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, pentaerythritol di(meth)acrylate,pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,pentaerythritol tri(meth)acrylate monooxalate, dipentaerythritoldi(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate mono(2-hydroxyethyl) ether, tripentaerythritolocta(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanedioldiitaconate, hexanediol di(meth)acrylate, 1,4-cyclohexanedioldi(meth)acrylate, sorbitol tri(meth)acrylate, sorbitoltetra(meth)acrylate, sorbitol penta(meth)acrylate, sorbitolhexa(meth)acrylate, oligoester(meth)acrylates, glycerol di(meth)acrylateand tri(meth)acrylate, di(meth)acrylates of polyethylene glycol with amolecular weight of from 200 to 1500, pentaerythritol diitaconate,dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate,dipentaerythritol hexaitaconate, ethylene glycol diitaconate, propyleneglycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanedioldiitaconate, tetramethylene glycol diitaconate, sorbitol tetraitaconate,ethylene glycol dicrotonate, tetramethylene glycol dicrotonate,pentaerythritol dicrotonate, ethylene glycol dimaleate, tiethyleneglycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate, ormixtures thereof.

Other examples are pentaerythritol and dipentaerythritol derivativesshown in the following formula (XII) and (XIII):

wherein

M₁₀ is —(CH₂CH₂O)— or —[CH₂CH(CH₃)O]—,

R₁₀₀ is —COCH═CH2 or —COC(CH₃)═CH₂,

p is 0 to 6 (total of p: 3-24), and q is 0 to 6 (total of q: 2-16).

Examples of polyepoxides are those based on the abovementioned polyolsand epichlorohydrin. Typical examples arebis(4-glycidyloxyphenyl)methane, 2,2-bis(4-glycidyloxyphenyl)propane,2,2-bis(4-glycidyloxyphenyl)hexafluoropropane,9,9-bis(4-glycidyloxyphenyl)fluorene,bis[4-(2-glycidyloxyethoxy)phenyl]methane,2,2-bis[4-(2-glycidyloxyethoxy)phenyl]propane,2,2-bis[4-(2-glycidyloxyethoxy)phenyl]hexafluoropropane,9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene,bis[4-(2-glycidyloxypropoxy)phenyl]methane,2,2-bis[4-(2-glycidyloxypropoxy)phenyl]propane,2,2-bis[4-(2-glycidyloxypropoxy)phenyl]hexafluoropropane,9,9-bis[4-(2-glycidyloxypropoxy)phenyl]fluorene, and glycidyl ethers ofphenol and cresol novolacs.

Typical examples of component (a) based on polyepoxides are2,2-bis[4-{(2-hydroxy-3-acryloxy)propoxy}phenyl]propane,2,2-bis[4-{(2-hydroxy-3-acryloxy)propoxyethoxy}phenyl]propane,9,9-bis[4-{(2-hydroxy-3-acryloxy)propoxy}phenyl]fluorene,9,9-bis[4-{(2-hydroxy-3-acryloxy)propoxyethoxy}phenyl]fluorine, andreaction products of epoxy resins based on novolacs with (meth)acrylicacid.

Polyethers obtained from the reaction of the abovementioned polyols orpolyepoxides with the unsaturated compounds with a hydroxy group such as2-hydroxyethyl(meth)acrylate, vinyl alcohol can also be used ascomponent (a).

Other examples for suitable components (a) are unsaturated urethanesderived from a polyisocyanate and an unsaturated compound having ahydroxy group or from a polyisocyanate, a polylol and an unsaturatedcompound having a hydroxy group.

Other examples are polyesters, polyamides, or polyurethanes havingethylenically unsaturated groups in the chain. Suitable unsaturatedpolyesters and polyamides are also derived, for example, from maleicacid and diols or diamines. Some of the maleic acid can be replaced byother dicarboxylic acids. The polyesters and polyamides may also bederived from dicarboxylic acids and ethylenically unsaturated diols ordiamines, especially from those with relatively long chains of, forexample 6 to 20 C atoms. Examples of polyurethanes are those composed ofsaturated or unsaturated diisocyanates and of unsaturated or,respectively, saturated diols.

Other suitable polymers with acrylate or methacrylate groups in the sidechains are, for example, solvent soluble or alkaline soluble polyimideprecursors, for example poly(amic acid ester) compounds, having thephotopolymerizable side groups either attached to the backbone or to theester groups in the molecule, i.e. according to EP 624826. Sucholigomers or polymers can be formulated optionally with reactivediluents, like polyfunctional (meth)acrylates in order to prepare highlysensitive polyimide precursor resists.

Further examples of the component (a) are also polymers or oligomershaving at least one carboxyl function and at least two ethylenicallyunsaturated groups within the molecular structure, such as a resinobtained by the reaction of a saturated or unsaturated polybasic acidanhydride with a product of the reaction of phenol or cresol novolacepoxy resin and an unsaturated monocarboxylic acid, for example,commercial products such as EB9696, UCB Chemicals; KAYARAD TCR1025,Nippon Kayaku Co., LTD. Examples of the polybasic acid anhydride aremaleic anhydride, succinic anhydride, itaconic anhydride, phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,methyltetrahydrophathalic anhydride, glutaric anhydride, glutaconicanhydride, citraconic anhydride, diglycolic anhydride, iminodiaceticanhydride, 1,1-cyclopentanediacetic anhydride, 3,3-dimethylglutaricanhydride, 3-ethyl-3-methylglutaric anhydride, 2-phenylglutaricanhydride, homophthalic anhydride, trimellitis anhydride, chlorendicanhydride, pyromellitic dianhydride, benzophenone tetracarboxylic aciddianhydride, biphenyl tetracarboxylic acid dianhydride, andbiphenylether tetracarboxylic acid dianhydride.

Other examples are the products from the polycondensation reactionand/or addition reaction of the compound of formula (XIV) with one ormore abovementioned polybasic acid anhydrides.

wherein Y₁₀ is

R₂₀₀ is hydrogen or methyl,

R₃₀₀ and R₄₀₀ independently of each other are hydrogen, methyl, CI, orBr, M₂₀ is substituted or unsubstituted alkylene having 1 to 10 carbonatoms, x is 0 to 5, and y is 1 to 10. Examples of such compounds ascomponent (a) are described in JP2002-206014A, JP2004-69754A,JP2004-302245A, JP2005-77451 A, JP2005-316449A, JP2005-338328A andJP3754065B2.

Polymers or oligomers as abovementioned have for example a molecularweight of about 1,000 to 1,000,000, preferably 2,000 to 200,000 and anacid value of about 10 to 200 mg KOH/g, preferably 20 to 180 mg KOH/g.

A preferred photopolymerizable composition comprises as component (a) acompound having at least two ethylenically unsaturated bonds and atleast one carboxylic acid group in the molecule, in particular areaction product obtained by adding an epoxy group containingunsaturated compound to a part of the carboxyl groups of a carboxylicacid group containing polymer or a reaction product of the compoundshown below with one or more polybasic acid anhydrides. Furtherpreferred components (a) comprise a compound obtained from the reactionof a compound of the formula XIV with one or more polybasic acidanhydrides.

Further examples are reaction products obtained by adding an epoxy groupcontaining unsaturated compound to a part of the carboxyl groups of acarboxylic acid group containing polymer. As the carboxylic acidcontaining polymer, the abovementioned binder polymers which areresulting from the reaction of an unsaturated carboxylic acid compoundwith one or more polymerizable compounds, for example, copolymers of(meth)acrylic acid, benzyl(meth)acrylate, styrene and2-hydroxyethyl(meth)acrylate, copolymers of (meth)acrylic acid, styreneand α-methystyrene, copolymers of (meth)acrylic acid, N-phenylmaleimide,styrene and benzyl(meth)acrylate, copolymers of (meth)acrylic acid andstyrene, copolymers of (meth)acrylic acid and benzyl(meth)acrylate,copolymers of tetrahydrofurfuryl(meth)acrylate, styrene and(meth)acrylic acid, and the like.

Examples of the unsaturated compounds having an epoxy group are givenbelow in the formula (V-1)-(V-15);

wherein R₅₀ is hydrogen or methyl group, M₃₀ is substituted orunsubstituted alkylene having 1 to 10 carbon atoms.

Among these compounds, compounds having alicyclic epoxy groups areparticularly preferred, because these compounds have a high reactivitywith carboxyl group-containing resins, accordingly the reaction time canbe shortened. These compounds further do not cause gelation in theprocess of reaction and make it possible to carry out the reactionstably. On the other hand, glycidyl acrylate and glycidyl methacrylateare advantageous from the viewpoint of sensitivity and heat resistancebecause they have a low molecular weight and can give a high conversionof esterification. Concrete examples of the abovementioned compoundsare, for example a reaction product of a copolymer of styrene, α-methylstyrene and acrylic acid or a copolymer of methyl methacrylate andacrylic acid with 3,4-epoxycyclohexylmethyl(meth)acrylate.

Unsaturated compounds having a hydroxy group such as2-hydroxyethyl(meth)acrylate and glycerol mono(meth)acrylate can be usedinstead of the above mentioned epoxy group containing unsaturatedcompounds as the reactant for carboxylic acid group containing polymers.

Other examples are half esters of anhydride containing polymers, forexample reaction products of a copolymer of maleic anhydride and one ormore other polymerizable compounds with (meth)acrylates having analcoholic hydroxy group such as 2-hydroxyethyl(meth)acrylate or havingan epoxy group for example such as the compounds described in theformula (V-1)-(V-15).

Reaction products of polymers having alcoholic hydroxy groups such ascopolymers of 2-hydroxyethyl(meth)acrylate, (meth)acrylic acid, benzymethacylate and styrene, with (meth)acrylic acid or (meth)acryl chloridecan also be used as component (a).

Other examples are reaction products of a polyester with terminalunsaturated groups, which is obtained from the reaction of a dibasicacid anhydride and a compound having at least two epoxy groups followedby further reaction with an unsaturated compound, with a polybasic acidanhydride.

Further examples are resins obtained by the reaction of a saturated orunsaturated polybasic acid anhydride with a reaction product obtained byadding epoxy group containing (meth)acrylic compound to all of thecarboxyl groups of a carboxylic acid containing polymer as mentionedabove.

The photopolymerizable compounds can be used alone or in any desiredmixtures.

In a color filter resist composition the whole amount of the monomerscontained in the photopolymerizable composition is preferably 5 to 80%by weight, in particular 10 to 70% by weight based on the whole solidcontents of the composition, i.e. the amount of all components withoutthe solvent(s).

As the binder used in the color filter resist composition, which issoluble in an alkaline aqueous solution and insoluble in water, forexample, a homopolymer of a polymerizable compound having one or moreacid groups and one or more polymerizable unsaturated bonds in themolecule, or a copolymer of two or more kinds thereof, and a copolymerof one or more polymerizable compounds having one or more unsaturatedbonds copolymerizable with these compounds and containing no acid group,can be used. Such compounds can be obtained by copolymerizing one ormore kinds of a low molecular compound having one or more acid groupsand one or more polymerizable unsaturated bonds in the molecule with oneor more polymerizable compounds having one or more unsaturated bondscopolymerizable with these compounds and containing no acid group.Examples of acids groups are, a —COOH group, a —SO₃H group, a —2NHCO—group, a phenolic hydroxy group, a —2NH— group, and a —CO—NH—CO— group.Among those, a high molecular compound having a —COOH group isparticularly preferred.

Preferably, the organic polymer binder in the color filter resistcomposition comprises an alkali soluble copolymer comprising, asaddition polymerizable monomer units, at least an unsaturated organicacid compound such as acrylic acid, methacrylic acid and the like. It ispreferred to use as a further co-monomer for the polymer binder anunsaturated organic acid ester compound such as methyl acrylate,ethyl(meth)acrylate, benzyl(meth)acrylate, styrene and the like tobalance properties such as alkaline solubility, adhesion rigidity,chemical resistance etc.

The organic polymer binder can either be a random co-polymer or ablock-co-polymer, for example, such as described in U.S. Pat. No.5,368,976.

Examples of the polymerizable compounds having one or more —COOH groupsand one or more polymerizable unsaturated bonds in a molecule are(meth)acrylic acid, 2-carboxyethyl(meth)acrylic acid,2-carboxypropyl(meth)acrylic acid, crotonic acid, cinnamic acid,mono[2-(meth)acryloyloxyethyl]succinate,mono[2-(meth)acryloyloxyethyl]adipate,mono[2-(meth)acryloyloxyethyl]phthalate,mono[2-(meth)acryloyloxyethyl]hexahydrophthalate,mono[2-(meth)acryloyloxyethyl]maleate,mono[2-(meth)acryloyloxypropyl]succinate,mono[2-(meth)acryloyloxypropyl]adipate,mono[2-(meth)acryloyloxypropyl]phthalate,mono[2-(meth)acryloyloxypropyl]hexahydrophthalate,mono[2-(meth)acryloyloxypropyl]maleate,mono[2-(meth)acryloyloxybutyl]succinate,mono[2-(meth)acryloyloxybutyl]adipate,mono[2-(meth)acryloyloxybutyl]phthalate,mono[2-(meth)acryloyloxybutyl]hexahydrophthalate,mono[2-(meth)acryloyloxybutyl]maleate, 3-(alkylcarbamoyl)acrylic acid,α-chloroacrylic acid, maleic acid, monoesterified maleic acid, fumaricacid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride,and ω-carboxypolycaprolactone mono(meth)acrylate.

Vinylbenzenesulfonic acid and 2-(meth)acrylamide-2-methylpropanesulfonicacid are examples of the polymerizable compounds having one or more—SO₃H groups and one or more polymerizable unsaturated bonds.

N-methylsulfonyl(meth)acrylamide, N-ethylsulfonyl(meth)acrylamide,N-phenylsulfonyl(meth)acrylamide, and N-(p-methylphenylsulfonyl)(meth)acrylamide are examples of the polymerizable compounds having oneor more —SO₂NHCO— groups and one or more polymerizable unsaturatedbonds.

Examples of polymerizable compounds having one or more phenolic hydroxygroups and one or more polymerizable unsaturated bonds in a moleculeinclude hydroxyphenyl(meth)acrylamide, dihydroxyphenyl(meth)acrylamide,hydroxyphenyl-carbonyloxyethyl(meth)acrylate,hydroxyphenyloxyethyl(meth)acrylate,hydroxyphenylthioethyl(meth)acrylate,dihydroxyphenylcarbonyloxyethyl(meth)acrylate, dihydroxyphenyloxyethyl(meth)acrylate, anddihydroxy-phenylthioethyl(meth)acrylate.

Examples of the polymerizable compounds having one or more —SO₂NH—groups and one or more polymerizable unsaturated bonds in the moleculeinclude compounds represented by formula (a) or (b):

CH₂═CHA₁₀₀-Y₁₀₀-A₂₀₀-SO₂—NH-A₃  (a)

CH₂═CHA₄₀₀-Y₂₀₀-A₅₀₀-NH—SO₂-A₆₀₀  (b)

wherein Y₁₀₀ and Y₂₀₀ each represents —COO—, —CONA₇₀₀-, or a singlebond; A₁₀₀ and

A₄₀₀ each represents H or CH₃; A₂₀₀ and A₅₀₀ each representsC₁-C₁₂alkylene optionally having a substituent, cycloalkylene, arylene,or aralkylene, or C₂-C₁₂alkylene into which an ether group and athioether group are inserted, cycloalkylene, arylene, or aralkylene;A₃₀₀ and A₆₀₀ each represents H, C₁-C₁₂alkyl optionally having asubstituent, a cycloalkyl group, an aryl group, or an aralkyl group; andA₇₀₀ represents H, C₁-C₁₂alkyl optionally having a substituent, acycloalkyl group, an aryl group, or an aralkyl group.

The polymerizable compounds having one or more —CO—NH—CO— group and oneor more polymerizable unsaturated bond include maleimide andN-acryloyl-acrylamide.

These polymerizable compounds become the high molecular compoundscomprising a —CO—NH—CO— group, in which a ring is formed together with aprimary chain by polymerization. Further, a methacrylic acid derivativeand an acrylic acid derivative each having a —CO—NH—CO— group can beused as well. Such methacrylic acid derivatives and the acrylic acidderivatives include, for example, a methacrylamide derivative such asN-acetylmethacrylamide, N-propionylmethacrylamide,N-butanoylmethacrylamide, Npentanoylmethacrylamide,N-decanoylmethacrylamide, N-dodecanoylmethacrylamide,N-benzoylmethacrylamide, N-(p-methylbenzoyl)methacryl-amide,N-(p-chlorobenzoyl)methacrylamide, N-(naphthyl-carbonyl)methacrylamide,N-(phenylacetyl)-methacrylamide, and 4-methacryloylaminophthalimide, andan acrylamide derivative having the same substituent as these. Thesepolymerizable compounds polymerize to be compounds having a —CO—NH—CO—group in a side chain.

Examples of polymerizable compounds having one or more polymerizableunsaturated bond and containing no acid group include a compound havinga polymerizable unsaturated bond, selected from esters of (meth)acrylicacid, such as methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl(meth)acrylate,tetrahydrofurfuryl(meth)acrylate, benzyl(meth)acrylate,2-ethylhexyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, glycerolmono(meth)acrylate, dihydroxypropyl(meth)acrylate, allyl(meth)acrylate,cyclohexyl(meth)acrylate, phenyl(meth)acrylate,methoxyphenyl(meth)acrylate, methoxyethyl(meth)acrylate,phenoxyethyl(meth)acrylate, methoxydiethyleneglycol(meth)acrylate,methoxytriethyleneglycol(meth)acrylate, methoxypropyl(meth)acrylate,methoxydipropyleneglycol(meth)acrylate, isobornyl meth(acrylate),dicyclopentadienyl(meth)acrylate,2-hydroxy-3-phenoxypropyl(meth)acrylate,tricyclo[5.2.1.0^(2,6)]decan-8-yl(meth)acrylate,aminoethyl(meth)acrylate, N, N-dimethylaminoethyl(meth)acrylate,aminopropyl(meth)acrylate, N, N-dimethylaminopropyl(meth)acrylate,glycidyl(meth)acrylate, 2-methylglycidyl(meth)acrylate,3,4-epoxybutyl(meth)acrylate, 6,7-epoxyheptyl(meth)acrylate; vinylaromatic compounds, such as styrene, α-methylstyrene, vinyltoluene,p-chlorostyrene, polychlorostyrene, fluorostyrene, bromostyrene,ethoxymethyl styrene, methoxystyrene, 4-methoxy-3-methystyrene,dimethoxystyrene, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether,indene, 1-methylindene; vinyl or allyl esters, such as vinyl acetate,vinyl propionate, vinyl butylate, vinyl pivalate, vinyl benzoate, vinyltrimethylacetate, vinyl diethylacetate, vinyl barate, vinyl caproate,vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinylbutoxyacetate, vinyl phenylacetate, vinyl acetate, vinyl acetoacetate,vinyl lactate, vinyl phenylbutylate, vinyl cyclohexylcarboxylate, vinylsalicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinylnaphthoate, allyl acetate, allyl propionate, allyl butylate, allylpivalate, allyl benzoate, allyl caproate, allyl stearate, allylacetoacetate, allyl lactate; vinyl or allyl ethers, such as vinyl methylether, vinyl ethyl ether, vinyl hexyl ether, vinyl octyl ether, vinylethylhexyl ether, vinyl methoxyethyl ether, vinyl ethoxyethyl ether,vinyl chloroethyl ether, vinyl hydroxyethyl ether, vinyl ethybutylether, vinyl hydroxyethoxyethyl ether, vinyl dimethylaminoethyl ether,vinyl diethylaminoethyl ether, vinyl butylaminoethyl ether, vinyl benzylether, vinyl tetrahydrofurfuryl ether, vinyl phenyl ether, vinyl tolylether, vinyl chlorophenyl ether, vinyl chloroethyl ether, vinyldichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, allylglycidyl ether; amide type unsaturated compounds, such as(meth)acrylamide, N, N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N, N-dibutyl(meth)acrylamide, N,N-diethylhexyl(meth)acrylamide, N, N-dicyclohexyl(meth)acrylamide, N,N-diphenyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide,N-hydroxyethyl-N-methyl(meth)acrylamide, N-methyl(meth)acrylamide,N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide,N-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide,N-heptyl(meth)acrylamide, N-octyl(meth)acrylamide,N-ethyhexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamidecyclohexyl,N-benzyl(meth)acrylamide, N-phenyl(meth)acrylamide,N-tolyl(meth)acrylamide, N-hydroxyphenyl(meth)acrylamide,N-naphthyl(meth)acrylamide, N-phenylsulfonyl(meth)acrylamide,N-methylphenylsulfonyl(meth)acrylamide and N(meth)acryloylmorpholine,diacetone acrylamide, N-methylol acrylamide, N-butoxyacrylamide;polyolefin type compounds, such as butadiene, isoprene, chloroprene andthe like; (meth)acrylonitrile, methyl isopropenyl ketone, maleimide,N-phenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide,N-cyclohexylmaleimide, N-alkylmaleimide, maleic anhydride, polystyrenemacromonomer, polymethyl(meth)acrylate macromonomer,polybutyl(meth)acrylate macromonomer; crotonates, such as butylcrotonate, hexyl crotonate, glycerine monocrotonate; and itaconates,such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate; andmaleates or fumarates, such as dimethyl mareate, dibutyl fumarate.

Preferable examples of copolymers are copolymers of methyl(meth)acrylateand (meth)acrylic acid, copolymers of benzyl(meth)acrylate and(meth)acrylic acid, copolymers of methyl(meth)acrylate/,ethyl(meth)acrylate and (meth)acrylic acid, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid and2-hydroxyethyl(meth)acrylate, copolymers of methyl(meth)acrylate/,butyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers ofmethyl(meth)acrylate, benzyl(meth)acrylate, (metha)crylic acid andhydroxyphenyl(meth)acrylate, copolymers of methyl(meth)acrylate,(meth)acrylic acid and polymethyl(meth)acrylate macromonomer, copolymersof benzyl(meth)acrylate, (meth)acrylic acid and polymethyl(meth)acrylatemacromonomer, copolymers of tetrahydrofurfuryl(meth)acrylate, styreneand (meth)acrylic acid, copolymers of methyl(meth)acrylate,(meth)acrylic acid and polystyrene macromonomer, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid and polystyrene macromonomer,copolymers of benzyl(meth)acrylate, (meth)acrylic acid,2-hydroxyethyl(meth)acrylate and polystyrene macromonomer, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid, 2-hydroxypropyl(meth)acrylateand polystyrene macromonomer, copolymers of benzyl(meth)acrylate,(meth)acrylic acid, 2-hydroxy-3-phenoxypropyl(meth)acrylate andpolymethyl(meth)acrylate macromonomer, copolymers ofmethyl(meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl(meth)acrylateand polystyrene macromonomer, copolymers of benzyl(metha)crylate,(meth)acrylic acid, 2-hydroxyethyl(meth)acrylate andpolymethyl(meth)acrylate macromonomer, copolymers of N-phenylmaleimide,benzyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid, N-phenylmaleimide,mono-[2-(meth)acryloyloxyethyl]succinate and styrene, copolymers ofallyl(meth)acrylate, (meth)acrylic acid, N-phenylmaleimide,mono-[2-(meth)acryloyloxyethyl]succinate and styrene, copolymers ofbenzyl(meth)acrylate, (meth)acrylic acid, N-phenylmaleimide, glycerolmono(meth)acrylate and styrene, copolymers of benzyl(meth)acrylate,ω-carboxypolycaprolactone mono(meth)acrylate, (meth)acrylic acid,N-phenylmaleimide, glycerol mono(meth)acrylate and styrene, andcopolymers of benzyl(meth)acrylate, (meth)acrylic acid,N-cyclohexylmaleimide and styrene.

There can be used as well hydroxystyrene homo- or co-polymers or anovolak type phenol resin, for example, poly(hydroxystyrene) andpoly(hydroxystyrene-co-vinylcyclohexanol), a novolak resin, a cresolnovolak resin, and a halogenated phenol novolak resin. Morespecifically, it includes, for example, the methacrylic acid copolymers,the acrylic acid copolymers, the itaconic acid copolymers, the crotonicacid co-polymers, the maleic anhydride co-polymers, for example, withstyrene as a co-monomer, and maleic acid copolymers, and partiallyesterified maleic acid copolymers each described in, for example, JP59-44615-B4 (the term “JP-B4” as used herein refers to an examinedJapanese patent publication), JP 54-34327-B4, JP 58-12577-B4, and JP54-25957-B4, JP 59-53836-A, JP 59-71048-A, JP 60-159743-A, JP60-258539-A, JP 1-152449-A, JP 2-199403-A, and JP 2-199404-A, and whichcopolymers can be further reacted with an amine, as e.g disclosed inU.S. Pat. No. 5,650,263; further, a cellulose derivative having acarboxyl group on a side chain can be used, and particularly preferredare copolymers of benzyl(meth)acrylate and (meth)acrylic acid andcopolymers of benzyl(meth)acrylate, (meth)acrylic acid and othermonomers, for example as described in U.S. Pat. No. 4,139,391, JP59-44615-B4, JP 60-159743-A and JP 60-258539-A.

With respect to those having carboxylic acid groups among the aboveorganic binder polymers, it is possible to react some or all of thecarboxylic acid groups with glycidyl(meth)acrylate or anepoxy(meth)acrylate to obtain photopolymerizable organic binder polymersfor the purpose of improving the photosensitivity, coating filmstrength, the coating solvent and chemical resistance and the adhesionto the substrate. Examples are disclosed in, JP 50-34443-B4 and JP50-34444-B4, U.S. Pat. No. 5,153,095, by T. Kudo et al. in J. Appl.Phys., Vol. 37 (1998), p. 3594-3603, U.S. Pat. No. 5,677,385, and U.S.Pat. No. 5,650,233.

The weight-average molecular weight of the binders is preferably 500 to1,000,000, e.g. 3,000 to 1,000,000, more preferably 5,000 to 400,000.

These compounds may be used singly or as a mixture of two or more kinds.The content of the binder in the light-sensitive resin composition ispreferably 10 to 95 weight %, more preferably 15 to 90 weight % based onthe whole solid matters.

Further, in the color filter the total solid component of each color maycontain an ionic impurity-scavenger, e.g. an organic compound having anepoxy group. The concentration of the ionic impurity scavenger in thetotal solid component generally is in the range from 0.1% by weight to10% by weight.

Examples of color filters, especially with respect to the abovedescribed combinations of pigments and ionic impurity scavenger aregiven in EP 320264. It is understood, that the photoinitiators accordingto the present invention, i.e. the compounds of the formula I in thecolor filter formulations described in EP 320264 can replace thetriazine initiator compounds.

The compositions according to this invention can comprise additionally acrosslinking agent which is activated by an acid, for example asdescribed in JP 10-221843A, and a compound which generates acidthermally or by actinic radiation and which activates a crosslinkingreaction.

The compositions according to this invention can also comprise latentpigments which are transformed into finely dispersed pigments during theheat treatment of the latent pigment containing photosensitive patternor coating. The heat treatment can be performed after exposure or afterdevelopment of the latent pigment-containing photoimageable layer. Suchlatent pigments are soluble pigment precursors which can be transformedinto insoluble pigments by means of chemical, thermal, photolytic orradiation induced methods as described, for example, in U.S. Pat. No.5,879,855. This transformation of such latent pigments can be enhancedby adding a compound which generates acid at actinic exposure or byadding an acidic compound to the composition. Therefore, a color filterresist can also be prepared, which comprises a latent pigment in acomposition according to this invention.

Examples for color filter resists, the composition of such resists andthe processing conditions are given by T. Kudo et al., Jpn. J. Appl.Phys. Vol. 37 (1998) 3594; T. Kudo et al., J. Photopolym. Sci. Technol.Vol 9 (1996) 109; K. Kobayashi, Solid State Technol. November 1992, p.S15-S18; U.S. Pat. No. 5,368,976; U.S. Pat. No. 5,800,952; U.S. Pat. No.5,882,843; U.S. Pat. No. 5,879,855; U.S. Pat. No. 5,866,298; U.S. Pat.No. 5,863,678; JP 06-230212A; EP320264; JP 09-269410A; JP 10-221843A; JP01-090516A; JP 10-171119A, U.S. Pat. No. 5,821,016, U.S. Pat. No.5,847,015, U.S. Pat. No. 5,882,843, U.S. Pat. No. 5,719,008, EP881541,or EP902327.

The photoinitiators of the present invention can be used in color filterresists, for example, such as those given as examples above, or canpartially or fully replace the known photoinitiators in such resists. Itis understood by a person skilled in the art that the use of the newphotoinitiators of the present invention is not limited to the specificbinder resins, crosslinkers and formulations of the color filter resistexamples given hereinbefore but can be used in conjunction with anyradically polymerizable component in combination with a dye or colorpigment or latent pigment to form a photosensitive color filter ink orcolor filter resist.

Accordingly, subject of the invention also is a color filter prepared byproviding red, green and blue (RGB) colour elements and, optionally ablack matrix, all comprising a photosensitive resin and a pigment on atransparent substrate and providing a transparent electrode either onthe surface of the substrate or on the surface of the color filterlayer, wherein said photosensitive resin comprises a polyfunctionalacrylate monomer, an organic polymer binder and a photopolymerizationinitiator of formula I or I′ as described above or a photoinitiatormixture of a compound of the formula I or I′. The monomer and bindercomponents, as well as suitable pigments are as described above. In themanufacture of color filters the transparent electrode layer can eitherbe applied on the surface of the transparent substrate or can beprovided on the surface of the red, green and blue picture elements andthe black matrix. The transparent substrate is for example a glasssubstrate which can additionally have an electrode layer on its surface.

It is preferred to apply a black matrix between the color areas ofdifferent color in order to improve the contrast of a color filter.

The photosensitive compositions of the present invention, as alreadystated above, are also suitable for the preparation of the black matrixof color filters. Said black matrix composition for example comprises

a photoinitiator compound of the formula I of the present invention,

an organic binder, in particular an organic binder, which is an epoxyacrylate resin having a carboxyl group,

a black coloring material,

a polymer dispersant, in particular a polymer dispersant containing abasic functional group.

The person skilled in the art is familiar with such formulations.Examples of suitable black matrix compositions and the components (otherthan the photoinitiator) as described above are given in JP Patent No.3754065, the disclosure of which hereby is incorporated by reference.

Instead of forming a black matrix using a photosensitive composition andpatterning the black photosensitive composition photolithographically bypatternwise exposure (i.e. through a suitable mask) to form the blackpattern separating the red green and blue coloured areas on thetransparent substrate it is alternatively possible to use an inorganicblack matrix. Such inorganic black matrix can be formed from deposited(i.e. sputtered) metal (i.e. chromium) film on the transparent substrateby a suitable imaging process, for example utilizing photolithographicpatterning by means of an etch resist, etching the inorganic layer inthe areas not protected by the etch resist and then removing theremaining etch resist.

There are different methods known how and at which step in the colorfilter manufacturing process the black matrix can be applied. It caneither be applied directly on the transparent substrate prior toformation of the red, green and blue (RGB) colour filter as alreadymentioned above, or it can be applied after the RGB colour filter isformed on the substrate.

In a different embodiment of a color filter for a liquid crystaldisplay, according to U.S. Pat. No. 626,796, the black matrix can alsobe applied on the substrate opposite to the RGB color filterelement-carrying substrate, which is separated from the former by aliquid crystal layer.

If the transparent electrode layer is deposited after applying the RGBcolor filter elements and—optionally—the black matrix, an additionalovercoat film as a protective layer can be applied on the color filterlayer prior to deposition of the electrode layer, for example, asdescribed in U.S. Pat. No. 5,650,263.

To form an overcoat layer of a color filter, photosensitive resin orthermosetting resin compositions are employed. The photosensitivecomposition of the present invention can also be used to form suchovercoat layers, because a cured film of the composition is excellent inflatness, hardness, chemical and thermal resistance, transparencyespecially in a visible region, adhesion to a substrate, and suitabilityfor forming a transparent conductive film, e.g., an ITO film, thereon.In the production of a protective layer, there has been a demand thatunnecessary parts of the protective layer, for example on scribing linesfor cutting the substrate and on bonding pads of solid image sensorsshould be removed from the substrate as described in JP57-42009A,JP1-130103A and JP1-134306A. In this regard, it is difficult toselectively form a protective layer with good precision using theabove-mentioned thermosetting resins. The photosensitive composition,however, allows to easily remove the unnecessary parts of the protectivelayer by photolithography.

It is obvious to those skilled in the art, that the photosensitivecompositions of the present invention can be used for generating red,green and blue color pixels and a black matrix, for the manufacture of acolor filter, regardless of the above described differences inprocessing, regardless, of additional layers which can be applied andregardless of differences in the design of the color filter. The use ofa composition according to the present invention to form coloredelements shall not be regarded as limited by different designs andmanufacturing processes of such color filters.

The photo-sensitive composition of the present invention can suitably beused for forming a color filter but will not be limited to thisapplication. It is useful as well for a recording material, a resistmaterial, a protective layer, a dielectric layer, in displayapplications and display elements, a paint, and a printing ink.

The photosensitive compositions according to the invention are alsosuitable for manufacturing interlayer insulating layers or dielectriclayers in a liquid crystal display, and more particularly in areflection type liquid crystal display including an active matrix typedisplay having a thin film transistor (TFT) as a switching device, and apassive matrix type without a switching device.

In recent years, liquid crystal displays have, for example, been widelyused for pocket-type TV sets and terminal devices for communication byvirtue of its small thickness and light weight. A reflection type liquidcrystal display without necessity of using a back light is in particularin demand because it is ultra-thin and light-weight, and it cansignificantly reduce power consumption. However, even if a back light isremoved out of a presently available transmission type color liquidcrystal display and a light reflection plate is added to a lower surfaceof the display, it would cause a problem in that the efficiency ofutilizing lights is low, and it is not possible to have practicalbrightness. As a solution to this problem, there have been suggestedvarious reflection type liquid crystal displays for enhancing anefficiency of utilizing lights. For instance, a certain reflection typeliquid crystal display is designed to include a pixel electrode havingreflection function.

The reflection type liquid crystal display includes an insulatingsubstrate and an opposing substrate spaced away from the insulatingsubstrate. A space between the substrates is filled with liquidcrystals. A gate electrode is formed on the insulating substrate, andboth the gate electrode and the insulating substrate are covered with agate insulating film. A semiconductor layer is then formed on the gateinsulating film above the gate electrode. A source electrode and a drainelectrode are also formed on the gate insulating film in contact withthe semiconductor layer. The source electrode, the drain electrode, thesemiconductor layer, and the gate electrode cooperate with one anotherto thereby constitute a bottom gate type TFT as a switching device.

An interlayer insulating film is formed covering the source electrode,the drain electrode, the semiconductor layer, and the gate insulatingfilm therewith. A contact hole is formed throughout the interlayerinsulating film on the drain electrode. A pixel electrode made ofaluminum is formed on both the interlayer insulating film and an innersidewall of the contact hole. The drain electrode of the TFT iseventually in contact with the pixel electrode through the interlayerinsulating film. The interlayer insulating layer is generally designedto have a roughened surface by which the pixel electrode acts as areflection plate which diffuses lights to get a wider angle for viewing(angle of visibility).

The reflection type liquid crystal display remarkably enhances anefficiency of using lights by virtue that the pixel electrode acts as alight reflection plate.

In the above-mentioned reflection type liquid crystal display, theinterlayer insulating film is designed to have projections and recessesby photolithography. To form and control a fine shape of the projectionsand recesses in micrometer order for surface roughness and to formcontact holes, photolithography methods using positive and negativephotoresists are used. For these resists the compositions according tothe invention are especially suitable.

The photosensitive compositions according to the invention can furtherbe used for manufacturing spacers, which control a cell gap of theliquid crystal part in liquid crystal display panels. Since theproperties of light transmitted or reflected through the liquid crystallayer in a liquid crystal display are dependent on the cell gap, thethickness accuracy and uniformity over the pixel array are criticalparameters for the performance of the liquid crystal display unit. In aliquid crystal cell, the spacing between the substrates in the cell ismaintained constant by sparsely distributing glass or polymer spheresabout several micrometers in diameter as spacers between the substrates.The spacers are thus held between the substrates to maintain thedistance between the substrates at a constant value. The distance isdetermined by the diameter of the spacers. The spacers assure theminimum spacing between the substrates; i.e., they prevent a decrease indistance between the substrates. However, they cannot prevent thesubstrates from being separated apart from each other, i.e. the increasein distance between the substrates. Additionally, this method of usingspacer beads has problems of the uniformity in the diameter of spacerbeads and difficulty in the even dispersion of spacer beads on thepanel, as well as nonuniform orientation and decrease in brightnessand/or optical aperture depending on the location of spacers on pixelarray region. Liquid crystal displays having a large image display areahave recently been attracting much attention. However, the increase inthe area of a liquid crystal cell generally produces the distortion ofthe substrates constituting the cell. The layer structure of the liquidcrystal tends to be destroyed due to the deformation of the substrate.Thus, even when spacers are used for maintaining the spacing between thesubstrates constant, a liquid crystal display having a large imagedisplay area is unfeasible because the display experiences disturbances.Instead of the above spacer sphere dispersion method, a method offorming columns in the cell gap as spacers has been proposed. In thismethod, columns of a resin are formed as spacers in the region betweenthe pixel array region and the counter electrode to form a prescribedcell gap. Photosensitive materials having adhesive properties withphotolithography are commonly used, for instance, in the manufacturingprocess of color filters. This method is advantageous compared with theconventional method using spacer beads in the points that location,number and height of the spacers may be controlled freely. In recentyears, as the spread of the touch panel type liquid crystal displayssuch as mobile audio players and handheld game platforms, the mechanicalstress to liquid crystal panel tends to grow. The demand for spacer thatcontrols the cell gap to raise mechanical strength becomes strong thusthe multi-spacer method is used. According to the multi-spacer method,when cell gap narrows by pressure from the outside, adding tomain-spacer that controls the cell gap normally lower sub-spacersupports the cell gap against external stress. The multi-spacer canfollow the contraction of liquid crystal at low temperature conditionsby main-spacer and prevent to generate bubbles inside the liquidcrystal.

The multi-spacer which contains main-spacer and sub-spacer is formed inthe same step using, for example, a halftone mask as described inJPA-2011065133. The photosensitive compositions according to theinvention are eligible for manufacturing process using halftone mask.

In a color liquid crystal display panel, such spacers are formed in thenonimaging area under black matrix of color filter elements. Therefore,the spacers formed using photosensitive compositions do not decreasebrightness and optical aperture.

Photosensitive compositions for producing protective layer with spacersfor color filters are disclosed in JP 2000-81701A and dry film typephotoresists for spacer materials are also disclosed in JP 11-174459Aand JP 11-174464A. As described in the documents, the photosensitivecompositions, liquid and dry film photoresists, are comprising at leastan alkaline or acid soluble binder polymer, a radically polymerizablemonomer, and a radical initiator. In some cases, thermally crosslinkablecomponents such as epoxide and carboxylic acid may additionally beincluded.

The steps to form spacers using a photosensitive composition are asfollows: a photosensitive composition is applied to the substrate, forinstance a color filter panel and after the substrate is prebaked, it isexposed to light through a mask. Then, the substrate is developed with adeveloper and patterned to form the desired spacers. When thecomposition contains some thermosetting components, usually a postbakingis carried out to thermally cure the composition.

The photocurable compositions according to the invention are suitablefor producing spacers for liquid crystal displays (as described above)because of their high sensitivity.

The photosensitive compositions according to the invention are alsosuitable for manufacturing microlens arrays used in liquid crystaldisplay panels, image sensors and the like.

Microlenses are microscopic passive optical components that fit onactive optoelectronic devices such as detectors, displays, and lightemitting devices (light-emitting diodes, transversal and vertical cavitylasers) to improve their optical input or output quality. The areas ofapplications are wide and cover areas such as telecommunications,information technology, audio-visual services, solar cells, detectors,solid-state light sources, and optical interconnects.

Present optical systems use a variety of techniques to obtain efficientcoupling between microlenses and microoptical devices.

The microlens arrays are used for condensing illuminating light on thepicture element regions of a nonluminescent display device, such as aliquid crystal display devices, to increase the brightness of thedisplay, for condensing incident light or as a means for forming animage on the photoelectric conversion regions of a line image sensorused for example in facsimiles and the like to improve the sensitivityof these devices, and for forming an image to be printed on aphotosensitive means used in liquid crystal printers or light emittingdiode (LED) printers.

The most common application is their use to improve the efficiency ofphotodetector arrays of a solid-state image sensing device such as acharge coupled device (CCD). In a detector array, the collection of asmuch light as possible in each detector element or pixel is wanted. If amicrolens is put on top of each pixel, the lens collects incoming lightand focuses it onto an active area that is smaller than the size of thelens.

According to the prior-art, microlens arrays can be produced by avariety of methods; for each of them compositions according to thepresent invention may be employed.

(1) A method for obtaining convex lenses wherein a pattern of the lensesin a planar configuration is drawn on a thermoplastic resin by aconventional photolithographic technique or the like, and then thethermoplastic resin is heated to a temperature above the softening pointof the resin to have flowability, thereby causing a sag in the patternedge (so called “reflowing”) (see, e.g., JP 60-38989A, JP 60-165623A, JP61-67003A, and JP 2000-39503A). In this method, when the thermoplasticresin used is photosensitive, a pattern of the lenses can be obtained byexposure of this resin to light.

(2) A method for forming a plastic or glass material by the use of amold or a stamper. As lens material, a photocurable resin and athermosetting resin can be used in this method (see, e.g., WO99/38035).

(3) A method for forming convex lenses on the basis of a phenomenon inwhich when a photosensitive resin is exposed to light in a desiredpattern by the use of an aligner, unreacted monomers move from theunexposed regions to the exposed regions, resulting in a swell of theexposed regions (see, e.g., Journal of the Research Group in MicroopticsJapanese Society of Applied Physics, Colloquium in Optics, Vol. 5, No.2, pp. 118-123 (1987) and Vol. 6, No. 2, pp. 87-92(1988)).

On the upper surface of a supporting substrate, a photosensitive resinlayer is formed. Thereafter, with the use of a separate shading mask,the upper surface of the photosensitive resin layer is illuminated withlight from a mercury lamp or the like, so that the photosensitive resinlayer is exposed to the light. As a result, the exposed portions of thephotosensitive resin layer swell into the shape of convex lenses to formthe light condensing layer having a plurality of microlens.

(4) A method for obtaining convex lenses wherein a photosensitive resinis exposed to light by a proximity exposure technique in which aphotomask is not brought into contact with the resin, to cause a blur atthe pattern edge, so that the amount of photochemical reaction productsis distributed depending upon the degree of blurring at the pattern edge(see, e.g., JP 61-153602A).

(5) A method for generating a lens effect wherein a photosensitive resinis exposed to light with a particular intensity distribution to form adistribution pattern of refractive index depending upon the lightintensity (see, e.g., JP 60-72927A and JP 60-166946A). Thephotosensitive compositions according to the invention can be used inany one of the above-mentioned methods to form microlens arrays usingphotocurable resin compositions.

A particular class of techniques concentrates on forming microlenses inthermoplastic resins like photoresist. An example is published byPopovic et al. in the reference SPIE 898, pp. 23-25 (1988). Thetechnique, named reflow technique, comprises the steps of defining thelenses' footprint in a thermoplastic resin, e.g. by photolithography ina photosensitive resin like a photoresist, and subsequently heating thismaterial above its reflow temperature. The surface tension draws theisland of photoresist into a spherical cap with a volume equal to theoriginal island before the reflow. This cap is a plano-convex microlens.Advantages of the technique are, amongst others, the simplicity, thereproducibility, and the possibility of integration directly on top of alight-emitting or light-detecting optoelectronic device.

In some cases, an overcoat layer is formed on the patterned lens unitswith a rectangular shape prior to reflowing to avoid a sagging of theisland of the resin in the middle without reflow into a spherical cap inthe reflow step. The overcoat acts as a permanent protective layer. Thecoating layer is also made of a photosensitive composition. Microlensarrays can also be fabricated by the use of a mold or a stamper as, forexample, disclosed in EP0932256. A process of manufacturing the planarmicrolens array is as follows: a release agent is coated on a shapingsurface of a stamper on which convex portions are densely arranged, anda photocurable synthetic resin material having a high refractive indexis set on the shaping surface of the stamper. Next, the base glass plateis pushed onto the synthetic resin material, thereby spreading thesynthetic resin material, and the synthetic resin material is cured byirradiating with ultraviolet radiation or by heating and is shaped toform the convex microlenses. Thereafter the stamper is peeled off. Then,a photocurable synthetic resin material having a low refractive index isadditionally coated onto the convex microlenses as an adhesive layer anda glass substrate which is made into a cover glass plate is pushed ontothe synthetic resin material, thereby spreading the same. The syntheticresin material is then cured and finally the planar microlens array isformed.

As disclosed in U.S. Pat. No. 5,969,867, a similar method using a moldis applied for the production of a prism sheet, which is used as a partof backlight units for color liquid crystal display panels to enhancethe brightness. A prism sheet forming a prism row on one side is mountedon the light-emitting surface of the backlight. For fabricating a prismsheet, an active energy ray-curable composition is cast and spread in alens mold which is made of metal, glass or resin and forms the lensshape of the prism row, etc., after which a transparent substrate sheetis placed onto it and active energy rays from an active energyray-emitting source are irradiated through the sheet for curing. Theprepared lens sheet is then released from the lens mold to obtain thelens sheet.

The active energy ray-curable composition used to form the lens sectionmust have a variety of properties, including adhesion to the transparentsubstrate, and suitable optical characteristics.

Lenses at least with some photoresists in the prior art are notdesirable for some applications since the optical transmittance in theblue end of the optical spectrum is poor. Because the photocurablecompositions according to the invention have low yellowing properties,both thermally and photochemically, they are suitable for the productionof microlens arrays as described above.

The novel radiation-sensitive compositions are also suitable forphoto-lithographic steps used in the production process of plasmadisplay panels (PDP), particularly for the imaging forming process ofbarrier rib, phosphor layer and electrodes.

The PDP is a planar display for displaying images and information byvirtue of the emission of light by gas discharge. By the construction ofpanel and the method of operation, it is known in two types, i.e. DC(direct current) type and AC (alternating current) type.

By way of example, the principle of the DC type color PDP will bebriefly explained. In the DC type color PDP, the space interveningbetween two transparent substrates (generally glass plates) is dividedinto numerous minute cells by latticed barrier ribs interposed betweenthe transparent substrates. In the individual cells a discharge gas,such as He or Xe, is sealed. On the rear wall of each cell there is aphosphor layer which, on being excited by the ultraviolet lightgenerated by the discharge of the discharge gas, emits visible light ofthree primary colors. On the inner faces of the two substrates,electrodes are disposed as opposed to each other across the relevantcells. Generally, the cathodes are formed of a film of transparentelectroconductive material such as NESA glass. When a high voltage isapplied between these electrodes formed on the fore wall and the rearwall, the discharge gas which is sealed in the cells induces plasmadischarge and, by virtue of the ultraviolet light radiated consequently,incites the fluorescent elements of red, blue, and green colors to emitlights and effect the display of an image. In the full-color displaysystem, three fluorescent elements severally of the three primary colorsof red, blue, and green mentioned above jointly form one pictureelement.

The cells in the DC type PDP are divided by the component barrier ribsof a lattice, whereas those in the AC type PDP are divided by thebarrier ribs which are arranged parallel to each other on the faces ofthe substrates. In either case, the cells are divided by barrier ribs.These barrier ribs are intended to confine the luminous discharge withina fixed area to preclude false discharge or cross talk between adjacentdischarge cells and ensure ideal display.

The compositions according to the invention also find application forthe production of one- or more-layered materials for the image recordingor image reproduction (copies, reprography), which may be mono- orpolychromatic. Furthermore the materials are suitable for color proofingsystems. In this technology formulations containing microcapsules can beapplied and for the image production the radiation curing can befollowed by a thermal treatment. Such systems and technologies and theirapplications are for example disclosed in U.S. Pat. No. 5,376,459.

The compounds of the formula I are also suitable as photoinitiators inthe holographic data storage application. Said photoinitiators generateradicals and initiate polymerization of monomer upon irradiation withblue laser radiation, suitable for holographic data storage. Thewavelength range of the blue laser is 390-420 nm, preferably 400-410 nmand particularly 405 nm. Holographic storage systems (holographicrecording media) are for example used to record and to retrieve a largeamount of data with fast access time. The photoinitiators of theinvention are for example in particular suitable for systems asdescribed for example in WO 03/021358.

The holographic data storage system is preferably comprised of a matrixnetwork of low-refractive index matrix precursors and high-refractiveindex photopolymerizable monomers.

The matrix precursor and photoactive monomer can be selected such that(a) the reaction by which the matrix precursor is polymerized during thecure is independent from the reaction by which the photoactive monomerwill be polymerized during writing of a pattern, e.g. data, and (b) thematrix polymer and the polymer resulting from polymerization of thephotoactive monomer (the photopolymer) are compatible with each other.The matrix is considered to be formed when the photorecording material,i.e. the matrix material plus the photoactive monomer, photoinitiatorand/or additives, exhibits an elastic modulus of at least about 10⁵ Pa,generally about 10⁵ Pa to about 10⁹ Pa.

The media matrix is formed by in-situ polymerization which yields ascross-linked network in the presence of the photopolymerizable monomerswhich remain “dissolved” and unreacted. The matrix containingun-reacted, photopolymerizable monomers can also be formed by othermeans, for example by using a solid-resin matrix material in which thephotoreactive, liquid monomer is homogeneously distributed. Then,monochromatic exposure generates the holographic pattern, whichaccording to the light intensity distribution, polymerizes thephotoreactive monomers in the solid pre-formed matrix. The unreactedmonomers (where light intensity was at a minimum) diffuse through thematrix, producing a modulation of the refractive index that isdetermined by the difference between the refractive indices of themonomer and the matrix and by the relative volume fraction of themonomer. The thickness of the recording layer is in the range of severalmicrometers up to a thickness of one millimeter. Because of such thickholographic data storage layers it is required that the photoinitiatorcombines high photoreactivity with low absorbance, in order to renderthe layer transparent at the laser wavelength to assure that the extentof photopolymerization is as little as possible dependent on theexposure depth into the recording layer.

It was found that the photoinitiators of the present invention combinehigh reactivity with low absorbance at 405 nm and are suitable for thisapplication. Dyes and sensitizers can also be added to the formulations.Suitable dyes and sensitizers for blue laser radiation are for examplecoumarines, xanthones, thioxanthones, see list above. In particularrelevant are thioxanthones, coumarins and benzophenones as mentionedunder items 1., 2. and 3. in the list given above.

It was found that the photoinitiators allow photopolymerization ofmonomers in thick layers, such as required for holographic data storage,with high sensitivity and yield recording layers which are sensitive toblue laser radiation. The photoinitiators, when applied at aconcentration of 2-8 wt % in the photosensitive layer of 20 micronthickness yield an absorbance of the layer which comprises thephotoinitiator, of less than 0.4, preferably less than 0.2 at the laserwavelength.

The photoinitiators are in particular suitable for the preparation ofoptical articles (for example optical waveguides) or holographicrecording media e.g. comprising a polymer and an organic photoinitiatoras described above, having a maximum absorption at a UV wavelength inthe range of 340-450 nm, wherein the refractive index contrast adjustedsensitivity is greater than 3×10⁻⁶ Δn/(mJ/cm²). For example, the polymeris formed by polymerizing a material comprising component 1 andcomponent 2, wherein component 1 comprises a NCO-terminated pre-polymerand component 2 comprises a polyol. Component 1 is, for example,diphenylmethane diisocyanate, toluene diisocyanate, hexamethylenediisocyanate, a derivative of hexamethylene diisocyanate, amethylenebiscyclohexylisocyanate, a derivative ofmethylenebiscyclohexylisocyanate. Component 2 is for example a polyol ofpropylene oxide. Preferably, the photoactive monomer is an acrylatemonomer. In such media the shrinkage induced by writing is usually lessthan 0.25%.

Photocuring further is of great importance for printings, since thedrying time of the ink is a critical factor for the production rate ofgraphic products, and should be in the order of fractions of seconds.UV-curable inks are particularly important for screen printing andoffset inks.

As already mentioned above, the novel mixtures are highly suitable alsofor producing printing plates. This application uses, for example,mixtures of soluble linear polyamides or styrene/butadiene and/orstyrene/isoprene rubber, polyacrylates or polymethyl methacrylatescontaining carboxyl groups, polyvinyl alcohols or urethane acrylateswith photopolymerizable monomers, for example acrylamides and/ormethacrylamides, or acrylates and/or methacrylates, and aphotoinitiator. Films and plates of these systems (wet or dry) areexposed over the negative (or positive) of the printed original, and theuncured parts are subsequently washed out using an appropriate solventor aqueous solutions.

Another field where photocuring is employed is the coating of metals, inthe case, for example, of the coating of metal plates and tubes, cans orbottle caps, and the photocuring of polymer coatings, for example offloor or wall coverings based on PVC.

Examples of the photocuring of paper coatings are the colourlessvarnishing of labels, record sleeves and book covers.

Also of interest is the use of the novel photoinitiators for curingshaped articles made from composite compositions. The composite compoundconsists of a self-supporting matrix material, for example a glass fibrefabric, or alternatively, for example, plant fibres [cf. K.-P. Mieck, T.Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated withthe photocuring formulation. Shaped parts comprising compositecompounds, when produced using the novel compounds, attain a high levelof mechanical stability and resistance. The novel compounds can also beemployed as photocuring agents in moulding, impregnating and coatingcompositions as are described, for example, in EP7086. Examples of suchcompositions are gel coat resins, which are subject to stringentrequirements regarding curing activity and yellowing resistance, andfibre-reinforced mouldings, for example, light diffusing panels whichare planar or have lengthwise or crosswise corrugation. Techniques forproducing such mouldings, such as hand lay-up, spray lay-up, centrifugalcasting or filament winding, are described, for example, by P. H. Seldenin “Glasfaserverstärkte Kunststoffe”, page 610, Springer VerlagBerlin-Heidelberg-New York 1967. Examples of articles which can beproduced by these techniques are boats, fibre board or chipboard panelswith a double-sided coating of glass fibre-reinforced plastic, pipes,containers, etc. Further examples of moulding, impregnating and coatingcompositions are UP resin gel coats for mouldings containing glassfibres (GRP), such as corrugated sheets and paper laminates. Paperlaminates may be based on urea resins or melamine resins. Prior toproduction of the laminate, the gel coat is produced on a support (forexample a film). The novel photocurable compositions can also be usedfor casting resins or for embedding articles, for example electroniccomponents, etc.

The compositions and compounds according to the invention can be usedfor the production of holographies, waveguides, optical switches whereinadvantage is taken of the development of a difference in the index ofrefraction between irradiated and unirradiated areas.

The use of photocurable compositions for imaging techniques and for theoptical production of information carriers is also important. In suchapplications, as already described above, the layer (wet or dry) appliedto the support is irradiated imagewise, e.g. through a photomask, withUV or visible light, and the unexposed areas of the layer are removed bytreatment with a developer. Application of the photocurable layer tometal can also be carried out by electrodeposition. The exposed areasare polymeric through crosslinking and are therefore insoluble andremain on the support. Appropriate colouration produces visible images.Where the support is a metallized layer, the metal can, followingexposure and development, be etched away at the unexposed areas orreinforced by electroplating. In this way it is possible to produceelectronic circuits and photoresists. When used in image-formingmaterials the novel photoinitiators provide excellent performance ingenerating so called printout images, whereby a color change is induceddue to irradiation. To form such printout images different dyes and/ortheir leuco form are used and examples for such print out image systemscan be fount e.g. in WO96/41240, EP706091, EP511403, U.S. Pat. No.3,579,339 and U.S. Pat. No. 4,622,286.

The novel photoinitiator is also suitable for a photopatternablecomposition for forming a dielectric layer of a multilayer layer circuitboard produced by a sequential build-up process.

The invention, as described above, provides compositions, as well as aprocess, for producing pigmented and nonpigmented paints and varnishes,powder coatings, printing inks, printing plates, adhesives, pressuresensitive adhesives, dental compositions, gel coats, photoresists forelectronics, etch resists, both liquid and dry films, solder resists,resists to manufacture color filters for a variety of displayapplications (a color filter resist contains pigments, pigments and dyes(i.e. hybrid systems) or dyes alone), resists to generate structures inthe manufacturing processes of plasma-display panels (e.g. barrier rib,phosphor layer, electrode), electroluminescence displays and LCD (e.g.interlayer insulating layers, spacers, multi-spacers, microlens arrays),for encapsulating electrical and electronic components, for producingmagnetic recording materials, micromechanical parts, waveguides, opticalswitches, plating masks, colour proofing systems, glass fibre cablecoatings, screen printing stencils, three-dimensional objects by meansof stereolithography, image recording materials for holographicrecordings (e.g. for holographic data storage (HDS)), microelectroniccircuits, decolorizing materials, formulations containing microcapsules,photoresist materials for a UV and visible laser direct imaging systemand for forming dielectric layers in a sequential build-up layer of aprinted circuit board; wherein the process comprises irradiating acomposition as described above with electromagnetic radiation in therange from 150 to 600 nm, or with electron beam or with X-rays.

Substrates used for photographic information recordings include, forexample, films of polyester, cellulose acetate or polymer-coated papers;substrates for offset printing formes are specially treated aluminium,substrates for producing printed circuits are copper-clad laminates, andsubstrates for producing integrated circuits are, for example, siliconwafers. The layer thickness of the photosensitive layer for photographicmaterials and offset printing forms is generally from about 0.5 μm to 10μm, while for printed circuits it is from 0.1 μm to about 100 μm.Following the coating of the substrates, the solvent is removed,generally by drying, to leave a coat of the photoresist on thesubstrate.

Coating of the substrates can be carried out by applying to thesubstrate a liquid composition, a solution or a suspension. The choiceof solvents and the concentration depend principally on the type ofcomposition and on the coating technique. The solvent should be inert,i.e. it should not undergo a chemical reaction with the components andshould be able to be removed again, after coating, in the course ofdrying. Examples of suitable solvents are ketones, ethers and esters,such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone,cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran,2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol,1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, ethyl3-ethoxypropionate, 2-methoxypropylacetate, methyl-3-methoxypropionate,2-heptanone, 2-pentanone, and ethyl lactate.

The solution is applied uniformly to a substrate by means of knowncoating techniques, for example by spin coating, dip coating, knifecoating, curtain coating, brushing, spraying, especially byelectrostatic spraying, and reverse-roll coating, and also by means ofelectrophoretic deposition. It is also possible to apply thephotosensitive layer to a temporary, flexible support and then to coatthe final substrate, for example a copper-clad circuit board, or a glasssubstrate by transferring the layer via lamination.

The quantity applied (coat thickness) and the nature of the substrate(layer support) are dependent on the desired field of application. Therange of coat thicknesses generally comprises values from about 0.1 μmto more than 100 μm, for example 0.1 μm to 1 cm, preferably 0.5 μm to1000 μm.

Following the coating of the substrates, the solvent is removed,generally by drying, to leave an essentially dry resist film of thephotoresist on the substrate.

The photosensitivity of the novel compositions can extend in generalfrom about 150 nm to 600 nm, for example 190-600 nm, (UV-vis region).Suitable radiation is present, for example, in sunlight or light fromartificial light sources. Consequently, a large number of very differenttypes of light sources are employed. Both point sources and arrays(“lamp carpets”) are suitable. Examples are carbon arc lamps, xenon arclamps, low-, medium-, high- and super high-pressure mercury lamps,possibly with metal halide dopes (metal-halogen lamps),microwave-stimulated metal vapour lamps, excimer lamps, superactinicfluorescent tubes, fluorescent lamps, argon incandescent lamps,electronic flashlights, photographic flood lamps, light emitting diodes(LED), electron beams and X-rays. The distance between the lamp and thesubstrate to be exposed in accordance with the invention may varydepending on the intended application and the type and output of lamp,and may be, for example, from 2 cm to 150 cm. Laser light sources, forexample excimer lasers, such as F₂ excimer lasers at 157 nm exposure,KrF excimer lasers for exposure at 248 nm and ArF excimer lasers forexposure at 193 nm are also suitable. Lasers in the visible region canalso be employed.

The term “imagewise” exposure includes both, exposure through aphotomask comprising a predetermined pattern, for example a slide, achromium mask, a stencil mask or a reticle, as well as exposure by meansof a laser or light beam, which for example is moved under computercontrol over the surface of the coated substrate and in this wayproduces an image. Suitable UV laser exposure systems for the purposeare, for example, provided by Etec and Orbotech (DP-100™ DIRECT IMAGINGSYSTEM). Other examples of laser light sources are, for example excimerlasers, such as F₂ excimer lasers at 157 nm exposure, KrF excimer lasersfor exposure at 248 nm and ArF excimer lasers for exposure at 193 nm.Further suitable are solid state UV lasers (e.g. Gemini from ManiaBarco,DI-2050 from PENTAX) and violet laser diodes with 405 nm output(DI-2080, DI-PDP from PENTAX). Lasers in the visible region can also beemployed. And the computer-controlled irradiation can also be achievedby electron beams. It is also possible to use masks made of liquidcrystals that can be addressed pixel by pixel to generate digitalimages, as is, for example, described by A. Bertsch, J. Y. Jezequel, J.C. Andre in Journal of Photochemistry and Photobiology A: Chemistry1997, 107, p. 275-281 and by K.-P. Nicolay in Offset Printing 1997, 6,p. 34-37.

Following the imagewise exposure of the material and prior todevelopment, it may be advantageous to carry out thermal treatment for ashort time. After the development a thermal post bake can be performedto harden the composition and to remove all traces of solvents. Thetemperatures employed are generally 50-250° C., preferably 80-220° C.;the duration of the thermal treatment is in general between 0.25 and 60minutes.

The photocurable composition may additionally be used in a process forproducing printing plates or photoresists as is described, for example,in DE4013358. In such a process the composition is exposed for a shorttime to visible light with a wavelength of at least 400 nm, without amask, prior to, simultaneously with or following imagewise irradiation.

After the exposure and, if implemented, thermal treatment, the unexposedareas of the photosensitive coating are removed with a developer in amanner known per se.

As already mentioned, the novel compositions can be developed by aqueousalkalis or organic solvents. Particularly suitable aqueous-alkalinedeveloper solutions are aqueous solutions of tetraalkylammoniumhydroxides or of alkali metal silicates, phosphates, hydroxides andcarbonates. Minor quantities of wetting agents and/or organic solventsmay also be added, if desired, to these solutions. Examples of typicalorganic solvents, which may be added to the developer liquids in smallquantities, are cyclohexanone, 2-ethoxyethanol, toluene, acetone andmixtures of such solvents. Depending on the substrate also solvents,e.g. organic solvents, can be used as developer, or, as mentioned abovemixtures of aqueous alkalis with such solvents. Particularly usefulsolvents for solvent development include methanol, ethanol, 2-propanol,1-propanol, butanol, diacetone alcohol, ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butylether, diethyleneglycol dimethyl ether, propyleneglycol monomethyl etheracetate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butylacetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone,cyclohexanone, 2-heptanone, 2-pentanone, epsilon-caprolactone,gamma-butylolactone, dimethylformamide, dimethylacetamide,hexamethylphosphoramide, ethyl lactate, methyl lactate,epsilon-caprolactam, and N-methyl-pyrrolidinone. Optionally, water canbe added to these solvents up to a level at which still a clear solutionis obtained and at which sufficient solubility of the unexposed areas ofthe light sensitive composition is maintained.

The invention therefore also provides a process for thephotopolymerization of compounds containing ethylenically unsaturateddouble bonds, i.e. monomeric, oligomeric or polymeric compoundscontaining at least one ethylenically unsaturated double bond, whichcomprises adding to these compounds at least one photoinitiator of theformula I as described above and irradiating the resulting compositionwith electromagnetic radiation, in particular light of the wavelength150 to 600 nm, in particular 190-600 nm, with electron beam, or withX-rays.

In other words, adding to these compounds compounds containingethylenically unsaturated double bonds at least one photoinitiator ofthe formula I as described above and irradiating the resultingcomposition with electromagnetic radiation, in particular light of thewavelength 150 to 600 nm, in particular 190-600 nm, with electron beam,or with X-rays.

The invention further provides a coated substrate which is coated on atleast one surface with a composition as described above, and describes aprocess for the photographic production of relief images, in which acoated substrate is subjected to imagewise exposure and then theunexposed portions are removed with a developer. Imagewise exposure maybe effected by irradiating through a mask or by means of a laser orelectron beam as already described above. Of particular advantage inthis context is the laser beam exposure already mentioned above.

The compounds of the invention have a good thermal stability, lowvolatility, good storage stability and high solubility, and are alsosuitable for photopolymerisations in the presence of air (oxygen).Further, they cause only low yellowing in the compositions afterphotopolymerization.

The examples which follow illustrate the invention in more detail,without restriciting the scope said examples only. Parts and percentagesare, as in the remainder of the description and in the claims, byweight, unless stated otherwise. Where alkyl radicals having more thanthree carbon atoms are referred to in the examples without any mentionof specific isomers, the n-isomers are meant in each case.

PREPARATION EXAMPLES Example 1 Synthesis of[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazole-8-yl]-{2-[6-(2-{[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazole-8-yl]-acetoxyimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-phenyl}-methanoneoxime O-acetate 1.a Synthesis of 11-(2-ethylhexyl)-11H-benzo[a]carbazole

11H-Benzo[a]carbazole can be prepared according to some procedures, forinstance, the procedure described in SYNLETT, 2006, 7, 1021. Thestructure is confirmed by the ¹H-NMR spectrum (CDCl₃). δ [ppm]: 7.29(td, 1H), 7.44 (td, 1H), 7.53 (td), 7.57-7.61 (m, 3H), 7.66 (d, 1H),8.01 (d, 1H), 8.11-8.15 (m, 3H), 8.77 (br, 1H).

To 11H-benzo[a]carbazole (0.70 g; 3.22 mmol) in dimethyl formamide (DMF)(3 mL) is added sodium hydride (0.19 g; 4.67 mmol) at 0° C. Afterstirring for 1 h at 0° C., 1-bromo-2-ethylhexane (1.24 g; 6.44 mmol) isadded at 0° C., and the mixture is stirred at room temperatureovernight. The reaction mixture is poured into ice-water, and the crudeproduct is extracted twice with AcOEt (acetic acid ethyl ester). Thecombined organic layer is washed with H₂O and brine, dried over MgSO₄,concentrated and dried in vacuo to give a yellow liquid as a crudeproduct (1.08 g). The product is used for the next reaction withoutfurther purification. The structure is confirmed by ¹H-NMR spectrum(CDCl₃). δ [ppm]:0.80-0.92 (m, 6H), 1.16-1.47 (m, 8H), 2.27 (m, 1H),4.65-4.69 (m, 2H), 7.27 (td, 1H), 7.44-7.59 (m, 4H), 7.66 (d, 1H), 8.02(d, 1H), 8.14 (d, 1H), 8.18 (d, 1H), 8.54 (d, 1H).

1.b Synthesis of[11-(2-ethylhexyl)-8-(2-fluorobenzoyl)-11H-benzo[a]carbazol-5-yl]-(2,4,6-trimethylphenyl)-methanone

To 11-(2-ethylhexyl)-11H-benzo[a]carbazole (47.16 g; 143.0 mmol) inCH₂Cl₂ (400 mL) are added 2,4,6-trimethylbenzoyl chloride (27.45 g;150.0 mmol) and AlCl₃ (20.00 g; 150.0 mmol) at 0° C. After stirring atroom temperature for 2 hours, AlCl₃ (22.93 g; 172.0 mmol) is added at 0°C. and 2-fluorobenzoyl chloride (23.78 g; 150.0 mmol) is added dropwise,and then the mixture is stirred at room temperature for 3 hours. Thereaction mixture is poured into ice-water, and the crude product isextracted twice with CH₂Cl₂. The combined organic layer is washed withwater and brine, dried over MgSO₄. After 230 ml of n-hexane are added,the CH₂Cl₂ is removed by concentration to give a beige solid. It iscollected by filtration, and washed with n-hexane. Then it is dried togive a beige solid (81.81 g; 95.7%). The structure is confirmed by¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.84 (t), 0.89 (t), 1.18-1.42 (m),2.20 (s), 2.28-2.31 (m), 2.40 (s), 4.72-4.76 (m), 6.96 (s), 7.19 (t),7.29 (t), 7.52-7.60 (m), 7.70-7.84 (m), 8.38 (s), 8.63-8.66 (m), 9.56(d); ¹⁹F-NMR spectrum (CDCl₃). δ [ppm]: −111.58.

1.c Synthesis of[2-(6-{2-[11-(2-Ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo-[a]carbazol-8-carbonyl]-phenoxy}-2,2,3,3,4,4,5,5-octafluoro-hexyloxy)-phenyl]-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-methanone

To[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11,11b-dihydro-4aH-benzo[a]carbazol-8-yl]-(2-fluoro-phenyl)-methanone(2.99 g; 5.00 mmol) in pyridine (15 mL) are added2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.59 g; 2.25 mmol) and sodiumhydride (0.40 g; 10.00 mmol) at room temperature. The mixture is heatedat 100° C., and it is stirred overnight. After it is cooled at roomtemperature, the reaction mixture is poured into ice-water. The crudeproduct is extracted twice with ethyl acetate. The combined organiclayer is washed with water and brine, dried over MgSO₄, and concentratedto give a brown solid. The crude product is purified by columnchromatography on silica gel eluting with a mixed solvent of CH₂Cl₂ andn-hexane (3:1) to give a yellow solid (0.74 g, 23%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]:0.80-0.92 (m), 1.16-1.47(m), 2.20 (m), 2.22 (d), 2.26-2.29 (m), 2.40 (d), 3.31 (m), 4.68 (t),4.74 (t), 6.97 (d), 7.12-7.31 (m), 7.47-7.59 (m), 7.68-7.83 (m), 8.31(d), 8.38 (s), 8.63 (t), 8.64 (s), 9.57 (m); ¹⁹F-NMR spectrum (CDCl₃). δ[ppm]: −123.96, −119.86

1.d Synthesis of[11-(2-Ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-{2-[6-(2-{[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]-hydroxyimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-phenyl}-methanoneoxime

To[2-(6-{2-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-carbonyl]-phenoxy}-2,2,3,3,4,4,5,5-octafluoro-hexyloxy)-phenyl]-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-methanone(0.74 g; 0.52 mmol) in pyridine (5 mL) is added hydroxylammoniumchloride (0.14 g; 2.08 mmol) at room temperature. The mixture is heatedto 100° C., and then the mixture is stirred overnight. After it iscooled to room temperature, the reaction mixture is poured intoice-water, and the crude is extracted twice with ethyl acetate. Thecombined organic layer is washed with water and brine, dried over MgSO₄,and concentrated to give an orange solid. The crude product is purifiedby column chromatography on silica gel eluting with a mixed solvent ofCH₂Cl₂ and n-hexane (1:1) to give a yellow solid (0.53 g, 36%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.80 (t),0.87 (t), 1.17-1.59 (m), 2.15 (s), 2.25 (m), 2.36 (s), 4.47 (m),4.66-4.70 (m), 6.90 (s), 7.07 (d), 7.20-7.26 (m), 7.44-7.84 (m), 7.56(d), 7.66-7.74 (m), 7.96 (s), 8.23 (s), 8.61 (d), 9.50 (s); ¹⁹F-NMRspectrum (CDCl₃). δ [ppm]: −127.77, −123.73

1.e[11-(2-Ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-{2-[6-(2-{[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-acetoxyimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-phenyl}-methanoneoxime O-acetate

To[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-{2-[6-(2-{[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-hydroxyimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-phenyl}-methanoneoxime (0.27 g; 0.19 mmol) in ethyl acetate (5 mL) are addedtriethylamine (0.19 g; 1.86 mmol) and acetyl chloride (0.15 g; 1.86mmol) at 0° C. The mixture is stirred for 4.5 hours. After the reactionis completed, the reaction mixture is added into water. Then, the crudeproduct is extracted with ethyl acetate. The combined organic layer iswashed with water and brine, dried over MgSO₄, and concentrated to givea yellow solid. The crude product is purified by column chromatographyon silica gel eluting with a mixed solvent of methanol and CH₂Cl₂ (2:98)to give a yellow solid (0.13 g; 46%). The structure is confirmed by¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.78 (t), 0.82 (t), 1.14-1.39 (m),1.99 (s), 2.17 (s), 2.22-2.25 (m), 2.35 (s), 4.49 (m), 4.67 (m),6.91-6.95 (m), 7.09-7.16 (m), 7.34-7.47 (m), 7.66-7.76 (m), 8.35 (s),8.43 (d), 8.61 (d), 9.52 (dd); ¹⁹F-NMR spectrum (CDCl₃). δ [ppm]:−123.82, −119.71

Example 2

Synthesis of1-(11-(2-ethylhexyl)-5-{4-[6-(4-{[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazol-5-yl]-acetoxyimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-benzoyl}-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-oneoxime O-acetate

2.a Synthesis of1-{11-(2-ethylhexyl)-5-[4-(6-{4-[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazole-5-carbonyl]-phenoxy}-2,2,3,3,4,4,5,5-octafluoro-hexyloxy)-benzoyl]-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-one

To1-[11-(2-ethylhexyl)-5-(4-fluoro-benzoyl)-11H-benzo[a]carbazol-8-yl]-3,5,5-trimethyl-hexan-1-one(1.18 g; 2.00 mmol) in pyridine (5 mL) are added2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.24 g; 0.90 mmol) and sodiumhydroxide (0.16 g; 4 mmol) at 80° C., and the mixture is stirred at 100°C. for 43 hours. After the reaction is completed, the reaction mixtureis cooled to room temperature, and poured into ice water. The crudeproduct is extracted with ethyl acetate, and the combined organic layeris washed with water and brine, dried over MgSO₄, and concentrated togive a yellow resin. The crude is purified by column chromatography onsilica gel eluting with a mixed solvent of CH₂Cl₂ and n-hexane (1:1) togive a yellow solid (0.40 g; 32%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 0.81-0.92 (m), 1.03 (d), 1.18-1.46 (m),2.27-2.35 (m), 2.89-2.96 (m), 3.02-3.08 (m), 4.60 (t), 4.74 (m), 7.06(d), 7.58 (m), 7.66 (t), 7.99 (m), 8.14 (dd), 8.33 (s), 8.43 (d), 8.61(d), 8.68 (d); ¹⁹F-NMR spectrum (CDCl₃). δ [ppm]: −123.32, −119.45.

2.b Synthesis of1-(11-(2-Ethylhexyl)-5-{4-[6-(4-{[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazol-5-yl]-hydroxylimino-methylyphenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-benzoyl}-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-oneoxime

To1-{11-(2-ethylhexyl)-5-[4-(6-{4-[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazole-5-carbonyl]-phenoxy}-2,2,3,3,4,4,5,5-octafluoro-hexyloxy)-benzoyl]-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-one(0.40 g; 0.28 mmol) in ethyl acetate (5 mL) and N-methylpyrrolidone(NMP) (0.5 mL) are added sodium acetate (94 mg; 1.14 mmol) andhydroxylammonium chloride (81 mg; 1.14 mmol) at 80° C. The mixture isstirred at 80° C. overnight. After the reaction is completed, thereaction mixture is cooled to room temperature, and poured intoice-water. The crude product is extracted with ethyl acetate. Thecombined organic layer is washed with water and brine, dried over MgSO₄,and concentrated to give an orange solid. The crude is purified bycolumn chromatography on silica gel eluting with a mixed solvent ofmethanol and CH₂Cl₂ (2:98) to give a yellow solid (0.18 g; 17%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.80-0.85(m), 0.88-0.92 (m), 1.17-1.48 (m), 1.93 (br), 2.28 (br), 2.88 (d), 4.59(t), 4.71 (br), 7.05 (d), 7.55-7.61 (m), 7.63-7.67 (m), 7.73 (d), 7.98(d), 8.25 (d), 8.55 (d), 8.61 (d); ¹⁹F-NMR spectrum (CDCl₃). δ [ppm]:−123.36, −119.36.

2.c Synthesis of1-(11-(2-ethylhexyl)-5-{4-[6-(4-{[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazol-5-yl]-acetoxylimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-benzoyl}-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-oneoxime O-acetate

To1-(11-(2-ethylhexyl)-5-{4-[6-(4-{[11-(2-ethylhexyl)-8-(3,5,5-trimethyl-hexanoyl)-11H-benzo[a]carbazol-5-yl]-hydroxylimino-methyl}-phenoxy)-2,2,3,3,4,4,5,5-octafluoro-hexyloxy]-benzoyl}-11H-benzo[a]carbazol-8-yl}-3,5,5-trimethyl-hexan-1-oneoxime (0.18 g; 0.13 mmol) in ethyl acetate (3 mL) are added triethylamine (0.13 g; 1.25 mmol) and acetyl chloride (0.10 g; 1.25 mmol) at 0°C. The mixture is stirred at room temperature for 6 hours. After thereaction is completed, the reaction mixture is added into ice-water.Then, the crude product is extracted with ethyl acetate. The combinedorganic layer is washed with water and brine, dried over MgSO₄, andconcentrated to give a yellow solid. The crude product is purified bycolumn chromatography on silica gel eluting with a mixed solvent ofmethanol and CH₂Cl₂ (0.5:99.5) to give a yellow solid (90 mg; 47%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.79-0.84(m), 0.89-0.93 (m), 1.18-1.43 (m), 1.93 (br), 2.24 (s), 2.28-2.30 (m),2.90-2.95 (m), 4.59 (t), 4.75-4.77 (m), 7.05 (d), 7.59 (d), 7.66 (t),7.87 (dd), 7.98 (d), 8.32 (s), 8.40 (s), 8.47 (d), 8.63 (d), ¹⁹F-NMRspectrum (CDCl₃). δ [ppm]: −123.35, −119.51.

Example 3 Synthesis of4-(11-(2-ethylhexyl)-5-{4-[3-(1-acetoxyimino-3-propoxycarbonyl-propyl)carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-acetoxyimino-butyricacid ethyl ester 3.a Synthesis of[11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-(4-fluorophenyl)-methanone

To 11-(2-ethylhexyl)-11H-benzo[a]carbazole (10.0 g, 30.6 mmol) in CH₂Cl₂(150 mL) are added 4-fluorobenzoyl chloride (5.03 g, 31.7 mmol) andAlCl₃ (4.58 g, 34.3 mmol) at 0° C. After stirring for 0.5 hour, thereaction mixture is stirred for 2 hours at room temperature. Thereaction mixture is poured into ice-water, and the crude product isextracted with CH₂Cl₂. The organic layer is washed with water and brine,dried over MgSO₄. After concentration, the crude product is purified bycolumn chromatography on silica gel eluting with a mixed solvent ofn-hexane and CH₂Cl₂ (1:1) to obtain an off-white solid (8.14 g; 57%).The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.83(t), 0.89 (t), 1.18-1.52 (m), 2.24-2.31 (m), 4.68-4.80 (m), 7.16 (t),7.31 (t), 7.50 (t), 7.55-7.60 (m), 7.65 (t), 7.97 (dd), 8.06 (d), 8.31(s), 8.50 (d), 8.65 (d); ¹⁹F-NMR spectrum (CDCl₃). δ [ppm]−106.30.

3.b Synthesis of4-(11-(2-Ethylhexyl)-5-(4-fluoro-benzoyl)-11H-benzo[a]carbazol-8-yl]-4-oxo-butyricacid ethyl ester

To compound the[11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-(4-fluorophenyl)methanone(4.025 g, 8.912 mmol) in CH₂Cl₂ (45 mL) are added ethylsuccinyl chloride(1.64 g, 10.0 mmol) and AlCl₃ (3.97 g, 29.8 mmol) at 0° C. Afterstirring for 0.5 hour, the reaction mixture is stirred for 2 hours atroom temperature. The reaction mixture is poured into ice-water, and thecrude product is extracted with CH₂Cl₂. The organic layer is washed withwater and brine, dried over MgSO₄. After concentration, the residue isrecrystallized with a mixed solvent of CH₂Cl₂ and n-hexane to obtain anoff-white solid (3.92 g; 76%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃) δ [ppm]: 0.83 (t), 0.89 (t), 1.18-1.50 (m), 2.24-2.32(m), 2.82 (t), 3.45 (t), 4.17 (q), 4.66-4.81 (m), 7.60 (d), 7.61 (t),7.68 (t), 7.99 (dd), 8.17 (d), 8.31 (s), 8.50 (d), 8.61 (d), 8.71 (s);¹⁹F-NMR spectrum (CDCl₃). δ [ppm]: −105.75.

3.c Synthesis of4-[5-(4-Carbazol-9-yl-benzoyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-8-yl]-4-oxo-butyricacid ethyl ester

To4-(11-(2-ethylhexyl)-5-(4-fluoro-benzoyl)-11H-benzo[a]carbazol-8-yl]-4-oxo-butyricacid ethyl ester (1.01 g, 1.75 mmol) in dimethylsulfoxide (DMSO) (10 mL)are added K₂CO₃ (738 mg, 5.33 mmol) and carbazole (297 mg, 1.77 mmol).The reaction mixture is heated to 150° C. and stirred overnight. Aftercooling to room temperature, the reaction mixture is poured into water,and the crude product is extracted with CH₂Cl₂. The organic layer iswashed with water and brine, dried over MgSO₄. After concentration, thecrude product is purified by column chromatography on silica gel elutingwith CH₂Cl₂ to obtain a brown resin (760 mg; 60%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.84 (t), 0.92 (t),1.20-1.52 (m), 2.28-2.36 (m), 2.82 (t), 3.48(t), 4.16 (q), 4.74-4.21(m), 7.33 (t), 7.46 (t), 7.60 (d), 7.63 (d), 7.68 (t), 7.72 (t), 7.77(d), 8.15 (t), 8.19 (d), 8.22 (d), 8.50 (s), 8.58 (d), 8.67 (d), 8.81(s).

3.d Synthesis of4-(11-(2-ethylhexyl)-5-{4-[3-(3-propoxycarbonyl-propionyl)-carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-oxo-butyricacid ethyl ester

To4-[5-(4-carbazol-9-yl-benzoyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-8-yl]-4-oxo-butyricacid ethyl ester (760 mg, 1.04 mmol) in CH₂Cl₂ (5 mL) are addedethylsuccinyl chloride (184 mg, 1.11 mmol) and AlCl₃ (737 mg, 5.52 mmol)at 0° C. After stirring for 0.5 hour, the reaction mixture is stirredfor 2 hours at room temperature. The reaction mixture is poured intoice-water, and the crude product is extracted with CH₂Cl₂. The organiclayer is washed with water and brine, dried over MgSO₄. Afterconcentration, the crude product is purified by column chromatography onsilica gel eluting with a mixed solvent of CH₂Cl₂ and AcOEt (10:1) toobtain off-white resin (257 mg; 30%). The structure is confirmed by¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.84 (t), 0.92 (t), 1.22-1.55 (m),2.30-2.38 (m), 2.84 (t), 3.49 (t), 4.12 (q), 4.16 (q), 4.71-4.88 (m),7.40 (t), 7.51 (t), 7.58-7.72 (m), 7.76 (d), 8.14 (d), 8.19 (d), 8.21(d), 8.25 (d), 8.50 (s), 8.60 (d), 8.67 (d), 8.82 (d).

3.e Synthesis of4-(11-(2-Ethylhexyl)-5-{4-[3-(1-hydroxyimino-3-propoxycarbonyl-propyl)-carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-hydroxyimino-butyricacid ethyl ester

To4-(11-(2-ethylhexyl)-5-{4-[3-(3-propoxycarbonyl-propionyl)-carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-oxo-butyricacid ethyl ester (257 mg, 0.295 mmol) in pyridine (10 mL) is addedhydroxylammonium chloride (62 mg, 0.89 mmol), and it is stirred at 80°C. for 5 hours. After it is cooled to room temperature, the reactionmixture is poured into water, and the crude product is extracted withethyl acetate. The organic layer is washed with water and brine, driedover MgSO₄. After concentration, the crude product is purified by columnchromatography on silica gel eluting with ethyl acetate to obtain anoff-white resin (260 mg; 95%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 0.83 (t), 0.90 (t), 1.20-1.53 (m), 2.25-2.33(m), 2.68 (t), 3.26 (t), 4.08 (q), 4.12 (q), 4.76-4.78 (m), 7.33 (t),7.46 (t), 7.56-7.84 (m), 8.16 (d), 8.20 (d), 8.36 (d), 8.44 (s), 8.65(d).

3.f Synthesis of4-(11-(2-ethylhexyl)-5-{4-[3-(1-acetoxyimino-3-propoxycarbonyl-propyl)-carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-acetoxyimino-butyricacid ethyl ester

To4-(11-(2-ethylhexyl)-5-{4-[3-(1-hydroxyimino-3-propoxycarbonyl-propyl)-carbazole-9-yl]-benzoyl}-11H-benzo[a]carbazol-8-yl)-4-hydroxyimino-butyricacid ethyl ester (260 mg, 0.289 mmol) in tetrahydrofurane (THF) (5 mL)are added triethylamine (86 mg, 0.84 mmol) and acetyl chloride (66 mg,0.84 mmol) at 0° C. After stirring for 1.5 hours, the reaction mixtureis poured into water, and the crude product is extracted with ethylacetate. The organic layer is washed with water and brine, dried overMgSO₄. After concentration, the crude product is purified by columnchromatography on silica gel eluting with ethyl acetate to obtain anoff-white resin (169 mg; 60%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 0.84 (t), 0.91 (t), 1.19-1.54 (m), 2.28 (s),2.31 (s), 2.60-2.69 (m), 3.27-3.35 (m), 4.09 (q), 4.14 (q), 4.73-4.85(m), 7.36 (t), 7.49 (t), 7.56-7.78 (m), 7.85 (d), 7.89 (d), 8.20 (d),8.22 (d), 3.23 (d), 8.49 (s), 8.53 (s), 8.60 (d), 8.67 (d).

Example 4 Synthesis of1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]hexane-1,6-dionedioxime O-diacetate 4.a Synthesis of1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]-hexane-1,6-dione

To 11-(2-ethylhexyl)-11H-benzo[a]carbazole (1.65 g; 5.00 mmol) in CH₂Cl₂(15 mL) are added 2,4,6-trimethylbenzoyl chloride (0.92 g; 5.11 mmol)and AlCl₃ (0.70 g; 5.25 mmol) at 0° C. After stirring at roomtemperature for 1 hour, AlCl₃ (0.70 g; 5.30 mmol) is added at 0° C. andadipoyl chloride (0.43 g; 2.33 mmol) is added dropwise, and then themixture is stirred at room temperature overnight. The reaction mixtureis poured into ice-water, and the crude product is extracted twice withCH₂Cl₂. The combined organic layer is washed with water and brine, driedover MgSO₄, and concentrated to give a green solid. The crude product ispurified by column chromatography on silica gel eluting with a mixedsolvent of CH₂Cl₂ and n-hexane (1:1) to give a beige solid (0.85 g;34.4%). The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]:0.82 (t, 6H), 0.89 (t, 6H), 1.17-1.42 (m, 16H), 1.93 (br, 4H), 2.21 (s,12H), 2.26 (m, 2H), 2.40 (s, 6H), 3.18 (br, 4H), 4.69 (m, 4H), 6.97 (s,4H), 7.54 (d, 2H), 7.69-7.78 (m, 4H), 8.08 (s, 2H), 8.39 (s, 2H), 8.61(br, 4H), 9.53 (d, 2H).

4.b Synthesis of1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]-hexane-1,6-dionedioxime

To1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-hexane-1,6-dione(0.85 g; 0.80 mmol) in pyridine (8 mL) is added hydroxylammounimchloride (0.23 g; 3.18 mmol) at 60° C., and the mixture is stirred at100° C. overnight. After the reaction is completed, the reaction mixtureis cooled at room temperature, and poured into ice-water. The crudeproduct is extracted with ethyl acetate. The combined organic layer iswashed with water and brine, dried over MgSO₄, and concentrated to givea yellow solid. The crude is purified by column chromatography on silicagel eluting with a mixed solvent of CH₂Cl₂ and n-hexane (3:1) to give ayellow solid (0.40 g; 46.2%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 0.79-0.86 (m, 12H), 1.15-1.38 (m, 16H), 1.70(br, 2H), 2.17 (s, 12H), 2.20 (m, 2H), 2.33 (s, 6H), 2.93 (br, 4H), 4.57(m, 4H), 6.92 (s, 4H), 7.41 (d, 2H), 7.61 (dd, 2H), 7.67-7.77 (m, 4H),8.14 (s, 2H), 8.34 (s, 2H), 8.58 (d, 2H), 9.55 (d, 2H).

4.c Synthesis of1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]hexane-1,6-dionedioxime O-diacetate

To1,6-bis-[11-(2-ethylhexyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-hexane-1,6-dionedioxime (0.40 g; 0.37 mmol) in dimethyl acetamide (5 mL) are addedtriethyl amine (0.12 g; 1.23 mmol) and acetyl chloride (0.09 g; 1.15mmol) at 0° C. The mixture is stirred at room temperature overnight.After the reaction is completed, the reaction mixture is added into icewater. Then, the crude product is extracted with ethyl acetate. Thecombined organic layer is washed with water and brine, dried over MgSO₄,and concentrated to give a beige powder. The crude product is purifiedby column chromatography on silica gel eluting with a mixed solvent ofCH₂Cl₂ and n-hexane (3:1) to give a yellow solid (0.35 g; 82%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.79-0.85(m, 12H), 1.18-1.33 (m, 16H), 1.72 (br, 4H), 2.19-2.22 (m, 20H), 2.35(s, 6H), 2.98 (br, 4H), 4.50 (m, 4H), 6.93 (s, 4H), 7.39 (d, 2H), 7.61(d, 2H), 7.68-7.78 (m, 4H), 8.25 (s, 2H), 8.34 (s, 2H), 8.55 (d, 2H),9.53 (d, 2H).

Example 5 Synthesis of1-[11-[4-(1-acetoxyimino-ethyl)-phenyl]-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-3-methyl-butan-1-oneoxime O-acetate 5.a Synthesis of1-(4-Benzo[a]carbazol-11-yl-phenyl)-ethanone

To 11H-benzo[a]carbazole (2.00 g, 9.22 mmol) in DMSO (20 mL) is addedK₂CO₃ (3.85 g, 27.9 mmol) at 180° C., and then the mixture is stirredfor 1 hour. To the mixture is added 4-fluoroacetophenone (1.28 g, 9.228mmol). After stirring for 8 hours, the reaction mixture is cooled toroom temperature, and poured into water. The crude product is extractedwith ethyl acetate, and it is washed with water and brine. The organiclayer is dried over MgSO₄. After concentration, the crude product ispurified by column chromatography on silica gel eluting with CH₂Cl₂ toobtain an off-white solid (160 mg; 5%). The structure is confirmed by¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.75 (s), 7.20 (d), 7.23 (t),7.34-7.46 (m), 7.65 (d), 7.75 (d), 8.00 (d), 8.19 (d), 8.22 (d), 8.25(d).

5.b Synthesis of1-{4-[5-(2,4,6-trimethyl-benzoyl)-benzo[a]carbazol-11-yl]-phenyl}-ethanone

To 1-(4-benzo[a]carbazol-11-yl-phenyl)-ethanone (649 mg, 1.93 mmol) inCH₂Cl₂ (10 mL) are added 2,4,6-trimethylbenzoyl chloride (369 mg, 2.02mmol) and AlCl₃ (1.50 g, 11.24 mmol) at 0° C. After stirring for 0.5hour, the reaction mixture is stirred for 2 hours at room temperature.The reaction mixture is poured into ice-water, and the crude product isextracted with CH₂Cl₂. The organic layer is washed with water and brine,dried over MgSO₄. After concentration, the crude product is purified bycolumn chromatography on silica gel eluting with a mixed solvent ofn-hexane and CH₂Cl₂ (1:1) to obtain an off-white solid (383 mg; 41%).The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.22(s), 2.41 (s), 2.77 (s), 6.97 (s), 7.15 (d), 7.30-7.34 (m), 7.39 (t),7.51 (d), 7.63 (d), 7.65 (d), 8.01 (d), 8.28 (d), 8.28 (d), 8.39 (s),9.53 (d).

5.c Synthesis of1-[11-(4-acetyl-phenyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]-3-methyl-butan-1-one

To1-{4-[5-(2,4,6-trimethyl-benzoyl)-benzo[a]carbazol-11-yl]-phenyl}-ethanone(383 mg, 0.795 mmol) in CH₂Cl₂ (10 mL) are added isovaleroyl chloride(120 mg, 0.995 mmol) and AlCl₃ (350 mg, 2.62 mmol) at 0° C. Afterstirring for 2 hours, the reaction mixture is poured into ice-water, andthe crude product is extracted with CH₂Cl₂. The organic layer is washedwith water and brine, dried over MgSO₄. After concentration, the crudeproduct is purified by column chromatography on silica gel eluting withCH₂Cl₂ to obtain an off-white solid (345 mg; 76%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.02 (d), 2.22 (s), 2.34(m), 2.43 (s), 2.78 (s), 2.94 (d), 7.00 (s), 7.14 (d), 7.33 (t), 7.48(d), 7.64-7.68 (m), 7.98 (d), 8.31 (d), 8.43 (s), 8.67 (s), 9.47 (d).

5.d Synthesis of1-[11-[4-(1-hydroxyimino-ethyl)-phenyl]-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-3-methyl-butan-1-oneoxime

To1-[11-(4-acetyl-phenyl)-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-3-methyl-butan-1-one(345 mg, 0.61 mmol) in pyridine (10 mL) is added hydroxylammoniumchloride (136 mg, 1.95 mmol), and it is stirred at 80° C. overnight.After it is cooled at room temperature, the reaction mixture is pouredinto ice-water, and the crude product is extracted with ethyl acetate.The organic layer is washed with water and brine, dried over MgSO₄.After concentration, the residue is recrystallized with a mixed solventof CH₂Cl₂ and n-hexane to obtain an off-white solid (345 mg; 76%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.94 (d),1.98 (m), 2.22 (s), 2.41 (s), 2.44 (s), 2.84 (d), 6.98 (s), 7.13 (d),7.32 (t), 7.54-7.59 (m), 7.64 (t), 7.96 (d), 8.22 (s), 8.40 (s), 9.48(d).

5.e Synthesis of1-[11-[4-(1-acetoxyimino-ethyl)-phenyl]-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]carbazol-8-yl]-3-methyl-butan-1-oneoxime O-acetate

To1-[11-[4-(1-hydroxyimino-ethyl)-phenyl]-5-(2,4,6-trimethyl-benzoyl)-11H-benzo[a]-carbazol-8-yl]-3-methyl-butan-1-oneoxime (290 mg, 0.50 mmol) in THF (10 mL) are added triethylamine (144mg, 1.42 mmol) and acetyl chloride (110 mg, 1.40 mmol) at 0° C. Afterstirring for 2 hours, the reaction mixture is poured into water, and thecrude product is extracted with ethyl acetate. The organic layer iswashed with water and brine, dried over MgSO₄. After concentration, thecrude product is purified by column chromatography on silica gel elutingwith a mixed solvent of CH₂Cl₂ and ethyl acetate (20:1) to obtain anoff-white solid (210 mg; 62%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 0.95 (s), 2.22 (s), 2.26 (s), 2.33 (s), 2.40(s), 2.55 (s), 2.87 (d), 6.98 (s), 7.12 (d), 7.33 (t), 7.56 (d),7.58-7.67 (m), 8.09 (d), 8.39 (s), 8.42 (s), 9.43 (d).

Examples 6-21

The compounds of the examples 6-21 are prepared according to the methodsas described above. The structures of the compounds are compiled intable 1.

TABLE 1 ¹H-NMR Ex- spectrum am- (CDCl₃) ple Structure δ [ppm]  6

0.58-0.74 (d), 0.75- 1.00 (m), 1.81 (m), 2.19 (s), 2.30 (s), 2.82 (d),4.78 (m), 7.56 (d), 7.76 (t), 7.84 (t), 7.89 (d), 8.23 (s), 8.68 (d),8.83 (s), 9.87 (d)  7

—  8

—  9

— 10

0.78-0.92 (m), 1.18- 1.34 (m), 1.87 (m), 2.14 (s), 2.25 (s), 2.30 (s),2.37 (s), 2.41 (s), 4.35 (m), 4.43 (m), 4.83 (w), 5.45 (s), 6.93 (s),7.18-7.36 (m), 7.37- 7.46 (m), 7.57 (t), 7.71 (t), 7.82 (t), 8.02 (d),8.27 (d), 8.29 (s), 8.35 (s), 8.39 (s), 8.48 (s) 11

— 12

1.15 (d), 1.91 (s), 2.02 (s), 2.16 (s), 2.38 (s), 2.39 (s), 3.45 (m),4.04 (m), 4.90 (m), 4.92 (m), 6.95 (s), 7.25-8.10 (m), 8.38 (m), 8.50(m), 9.52 (m) 13

1.11 (m), 1.51 (m), 1.78 (m), 2.22 (s), 2.26 (s), 2.48 (t), 2.90 (t),4.00 (t), 4.88 (t), 7.12 (t), 7.52-7.64 (m), 7.75 (d), 7.81 (d), 8.43(s), 8.50 (s), 8.51 (d), 8.55 (d) 14

0.95 (d), 1.12 (d), 1.96 (m), 2.22 (m), 2.26 (s), 2.84 (d), 2.86 (d),7.29 (d), 7.34 (d), 7.40 (t), 7.51 (d), 7.53 (d), 7.60 (d), 7.67 (t),7.78 (d), 7.80 (d), 7.95 (d), 8.35 (s), 8.39 (d), 8.42 (s) 15

— 16

0.82 (t), 0.88 (t), 1.36-1.48 (m), 2.13 (s), 2.26 (s), 2.38 (s), 2.39(s), 4.74 (m), 7.31 (d), 7.34 (d), 7.39 (d), 7.48 (d), 7.52 (d), 7.53-7.68 (m), 7.76 (d), 7.77 (d), 7.83 (d), 8.28 (s), 8.33 (s), 8.42 (d),8.62 (d) 17

— 18

0.79-1.00 (m), 1.18- 1.56 (m), 2.04 (s), 2.20 (s), 2.29 (s), 2.31 (s),2.33 (s), 2.36 (s), 2.64 (q), 3.30 (q), 4.12 (m), 4.78 (m), 6.92 (s),6.94 (s), 7.34-7.42 (m), 7.44- 7.58 (m), 7.66 (d), 7.67 (t), 7.70-7.86(m), 7.88 (d), 8.09 (s), 8.18 (d), 8.22 (d), 8.34 (s), 8.40 (s), 8.52(s), 8.53 (s), 8.56 (s), 8.65 (d), 8.68 (d), 9.53 (d), 9.55 (d) 19

— 20

— 21

0.78-0.96 (m), 1.12- 1.28 (m), 1.92 (s), 1.98 (s), 2.09 (s), 2.19 (s),2.31 (s), 2.71 (s), 3.08 (m), 3.04 (m), 3.88 (m), 4.51-4.58 (m), 6.90-7.06 (m), 7.14-7.48 (m), 7.62- 7.74 (m), 7.76-7.98 (m), 8.00 (s), 8.23(s), 8.29 (d), 8.60 (d), 9.44 (d)

APPLICATION EXAMPLES Example A1 Preparation ofpoly(benzylmethacrylate-co-methacrylic acid)

24 g of benzylmethacrylate, 6 g of methacrylic acid and 0.525 g ofazobisisobutyronitrile (AIBN) are dissolved in 90 ml of propylene glycol1-monomethyl ether 2-acetate (PGMEA). The resulting reaction mixture isplaced in a preheated oil bath at 80° C. After stirring for 5 hours at80° C. under nitrogen, the resulting viscous solution is cooled to roomtemperature and used without further purification. The solid content isabout 25%.

Example A2 Sensitivity Tests a Photocurable Composition for aSensitivity Test is Prepared by Mixing the Following Components

-   200.0 parts by weight of copolymer of benzylmethacrylate and    methacrylic acid (benzylmethacrylate: methacrylic acid=80:20 by    weight) 25% propylene glycol 1-monomethyl ether 2-acetate (PGMEA)    solution, prepared in above example A1-   50.0 parts by weight of dipentaerythritol hexaacrylate ((DPHA),    provided by UCBChemicals),-   1.0 parts by weight of photoinitiator-   150.0 parts by weight of PGMEA

All operations are carried out under yellow light. The compositions areapplied to an aluminum plate using an electric applicator with a wirewound bar. The solvent is removed by heating at 80° C. for 10 minutes ina convection oven. The thickness of the dry film is approximately 2 μm.A standardized test negative film with 21 steps of different opticaldensity (Stouffer step wedge) is placed with an air gap of around 100 μmbetween the film and the resist. A glass filter (UV-35) is placed on thenegative film. Exposure is carried out using a 250W super high pressuremercury lamp (USHIO, USH-250BY) at a distance of 15 cm. A total exposuredose measured by an optical power meter (ORC UV Light Measure ModelUV-M02 with UV-35 detector) on the glass filter is 1000 mJ/cm². Afterexposure, the exposed film is developed with an alkaline solution (5%aqueous solution of DL-A4, Yokohama Yushi) for 120 sec. at 28° C. byusing a spray type developer (AD-1200, Takizawa Sangyo). The sensitivityof the initiator used is characterized by indicating the highest numberof the step remained (i.e. polymerized) after developing. The higher thenumber of steps, the more sensitive is the initiator tested. The resultsare listed in table 2.

TABLE 2 photoinitiator of example number of steps 1 19 2 19 3 19

Example A3 Sensitivity Tests

A photocurable composition for a sensitivity test is prepared by mixingthe following components:

-   11.0 parts by weight of REGAL® 400 pigment black (provided by CABOT)-   11.0 parts by weight of EFKA® 4046, dispersant (provided by BASF)-   10.3 parts by weight of Ripoxy® SPC1000, binder polymer (provided by    SHOWA DENKO)-   3.6 parts by weight of dipentaerythritol penta-/hexa-acrylate    ((DPHA), provided by SIGMA-ALDRICH)-   1.0 parts by weight of photoinitiator-   48.5 parts by weight of propylene glycol monomethyl ether acetate    (PGMEA)-   15.6 parts by weight of cyclohexanone

All operations are carried out under yellow light. The compositions areapplied to a glass plate using spincoater. The solvent is removed byheating at 80° C. for 10 minutes in a convection oven. The thickness ofthe dry film is approximately 1.4 μm. A step-wedge pattern mask with 9linear steps and 9 logarithmic steps of different optical density(Edumund Optics, EIA GrayScale Pattern Slide) is placed on the resistdirectly. Exposure is carried out using a 250 W super high pressuremercury lamp (USHIO, USH-250BY) at a distance of 15 cm. A total exposuredose measured by an optical power meter (ORC UV Light Measure ModelUV-M02 with UV-35 detector) on the glass filter is 500 mJ/cm². Afterexposure, the exposed film is developed with an alkaline solution (5%aqueous solution of DL-A4, YOKOHAMA OILS & FATS) for 10 seconds afterbreak time at 28° C. by using a spray type developer (AD-1200, MIKASA).Break time is the development time of unexposured region. The necessaryUV dose for full curing (i.e. the pattern is not dissolved with thealkaline solution) is calculated from the residual thickness of eachstep after development. The smaller the value of the dose, the moresensitive is the tested initiator. The results are listed in Table 3.

TABLE 3 photoinitiator of The necessary UV dose for example UV fullcuring  4 32 mJ/cm²  5 23 mJ/cm² 10 51 mJ/cm² 13 59 mJ/cm² 16 54 mJ/cm²18 41 mJ/cm² 21 53 mJ/cm² Irgacure ® OXE02 80 mJ/cm² Irgacure ®OXE 02 isethanone,1-[9-ethyl-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)

1. A compound of formula (I):

wherein: R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ independently ofeach other are hydrogen, C₁-C₂₀alkyl,

COR₁₄, NO₂, or OR₁₅, provided that at least one of R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, and R₁₀ is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄ or NO₂; X is CO or a direct bond; R₁₁ isC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, orM; or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈ or M; or R₁₁ is C₆-C₂₀aryl orC₃-C₂₀heteroaryl each of which is unsubstituted or substituted by one ormore phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or NR₁₇R₁₈; R₁₂ is hydrogen,C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy or C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, phenyl,C₁-C₂₀alkylphenyl or CN, or R₁₂ is phenyl or naphthyl, each of which isunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl,halogen, CN, OR₁₅, SR₁₆, or NR₁₇R₁₈, or R₁₂ is C₃-C₂₀heteroaryl,benzyloxy or phenoxy, each of which is unsubstituted or substituted byone or more C₁-C₆alkyl, C₁-C₄haloalkyl and/or halogen; R₁₃ is C₆-C₂₀arylor C₃-C₂₀heteroaryl each of which is unsubstituted or substituted by oneor more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈,PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl, SO₂—C₁-C₁₀alkyl, M, or byC₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O),phenylene, naphthylene or by NR₁₉, or each of which is substituted byone or more C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore halogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl,C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl,OR₁₅, SR₁₆, NR₁₇R₁₈ or by M, or R₁₃ is C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, OR₁₅, SR₁₆,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, NR₁₇R₁₈, COOR₁₅, CONR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂,

phenyl or by M, or R₁₃ is C₁-C₂₀alkyl which is substituted by phenylwhich is substituted by one or more halogen, C₁-C₂₀alkyl,C₁-C₄haloalkyl, OR₁₅, SR₁₆ or by NR₁₇R₁₈, or R₁₃ is C₂-C₂₀alkyl which isinterrupted by one or more O, CO, S, C(O)O, OC(O), phenylene,naphthylene, or NR₁₉, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₅, COOR₁₅,CONR₁₇R₁₈, phenyl, M, or by phenyl which is substituted by OR₁₅, SR₁₆ orNR₁₇R₁₈, or R₁₃ is CN, CONR₁₇R₁₈, NO₂, C₁-C₄haloalkyl,S(O)_(m)—C₁-C₆alkyl; S(O)_(m)-phenyl which is unsubstituted orsubstituted by C₁-C₁₂alkyl or SO₂—C₁-C₆alkyl, or R₁₃ phenyl which isunsubstituted or substituted by C₁-C₁₂alkyl; or is diphenyl phosphinoylor di-(C₁-C₄alkoxy)-phosphinoyl; M is

k is an integer 1-10; m is 1 or 2; R′₁₂ has one of the meanings as givenfor R₁₂; R′₁₃ has one of the meanings as given for R₁₃; R″₁₃ isC₁-C₂₀alkyl which is unsubstituted or substituted by phenyl or by phenylwhich is substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆or by NR₁₇R₁₈, or R″₁₃ is C₂-C₂₀alkyl which is interrupted by one ormore O, CO, S, C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, or by phenyl which issubstituted by OR₁₅, SR₁₆ or NR₁₇R₁₈, or R″₁₃ is CN, CONR₁₇R₁₈, NO₂,C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl; S(O)_(m)-phenyl which isunsubstituted or substituted by C₁-C₁₂alkyl or SO₂—C₁-C₆alkyl, or R″₁₃is SO₂O-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl; oris diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl, or R″₁₃ isC₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR₁₉, or each ofwhich is substituted by one or more C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or by NR₁₇R₁₈; X₁ is O, CO, S ora direct bond; X₂ is O, S, SO or SO₂; X₃ is O, S or NR₁₉; R₁₄ isC₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₅, SR₁₆, NR₁₇R₁₈, or by C₂-C₂₀alkyl which is interrupted by one ormore O, S, or NR₁₉, or each of which is substituted by one or moreC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ orNR₁₇R₁₈, or R₁₄ is

R₁₅ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OH, SH, CN, C₃-C₆alkenoxy,OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl),C₃-C₂₀cycloalkyl, SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl),O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which is interrupted by oneor more O, or R₁₅ is C₂-C₂₀alkyl which is interrupted by one or more O,S or NR₁₉, which interrupted C₂-C₂₀alkyl is unsubstituted or substitutedby O—C₆-C₂₀arylene-M, or R₁₅ is (CH₂CH₂O)_(n+1)H,(CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₁-C₈alkanoyl, C₂-C₁₂alkenyl,C₃-C₆alkenoyl or C₃-C₂₀cycloalkyl which is uninterrupted or interruptedby one or more O, S, CO or NR₁₉, or R₁₅ is C₁-C₈alkyl-C₃-C₁₀cycloalkylwhich is uninterrupted or interrupted by one or more O, or R₁₅ isbenzoyl which is unsubstituted or substituted by one or more C₁-C₆alkyl,halogen, OH or C₁-C₃alkoxy, or R₁₅ is phenyl, naphthyl orC₃-C₂₀heteroaryl, each of which is unsubstituted or substituted by oneor more halogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, CN, NO₂,phenyl-C₁-C₃alkyloxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,N(C₁-C₁₂alkyl)₂, diphenylamino or

n is 1-20; R₁₆ is hydrogen, C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, orphenyl-C₁-C₃alkyl, wherein the C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, orphenyl-C₁-C₃alkyl is uninterrupted or interrupted by one or more O, S,CO, NR₁₉, or R₁₆ is C₁-C₂₀alkyl which is unsubstituted or is substitutedby one or more OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl),O(CO)-phenyl or COOR₁₅ or S—C₆-C₂₀arylene-S-M, or R₁₆ is C₂-C₂₀alkylwhich is interrupted by one or more O, S, CO, NR₁₉, which interruptedC₂-C₂₀alkyl is unsubstituted or substituted by S—C₆-C₂₀arylene-M, or R₁₆is (CH₂CH₂O)_(n)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₂-C₈alkanoyl orC₃-C₆alkenoyl, or R₁₆ is benzoyl which is unsubstituted or substitutedby one or more C₁-C₆alkyl, halogen, OH, C₁-C₄alkoxy orC₁-C₄alkylsulfanyl, or R₁₆ is phenyl, naphthyl or C₃-C₂₀heteroaryl, eachof which is unsubstituted or substituted by one or more halogen,C₁-C₁₂alkyl, C₁-C₄haloalkyl, C₁-C₁₂alkoxy, CN, NO₂,phenyl-C₁-C₃alkyloxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,N(C₁-C₁₂alkyl)₂, diphenylamino, (CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl,(CO)N(C₁-C₈alkyl)₂ or

R₁₇ and R₁₈ independently of each other are hydrogen, C₁-C₂₀alkyl,C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl, C₃-C₂₀cycloalkyl,phenyl-C₁-C₃alkyl, C₈alkanoyl, C₁-C₈alkanoyloxy, C₃-C₁₂alkenoyl,SO₂—(C₁-C₄haloalkyl) or benzoyl, or R₁₇ and R₁₈ are phenyl, naphthyl orC₃-C₂₀heteroaryl, each of which is unsubstituted or substituted by oneor more halogen, C₁-C₄haloalkyl, C₁-C₂₀alkoxy, C₁-C₁₂alkyl, benzoyl orC₁-C₁₂alkoxy, or R₁₇ and R₁₈ together with the N-atom to which they areattached form a 5- or 6-membered saturated or unsaturated ring which isuninterrupted or is interrupted by O, S or NR₁₉, and which 5- or6-membered saturated or unsaturated ring is unsubstituted or substitutedby one or more C₁-C₂₀alkyl, C₁-C₂₀alkoxy, ═O, OR₁₅, SR₁₆, NR₂₈R₂₉,COR₃₀, NO₂, halogen, C₁-C₄-haloalkyl, CN, phenyl,

or by C₃-C₂₀cyclalkyl which is uninterrupted or is interrupted by one ormore O, S, CO or NR₁₉, or R₁₇ and R₁₈ together with the N-atom to whichthey are attached form a group

R₁₉ is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO, C(O)O, or OC(CO), or isphenyl-C₁-C₄alkyl, C₃-C₈cycloalkyl which is uninterrupted or isinterrupted by one or more 0 or CO, or R₁₉ is COR₃₀, or R₁₉ is phenyl ornaphthyl both of which are unsubstituted or substituted by one or moreC₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, COR₁₄, or

or R₁₉ is C₁-C₆alkylene or C₂-C₆alkenylene linked to the phenyl ornaphthyl ring of the carbazole moiety and forming a 5- or 6-memberedsaturated or unsaturated ring; R₂₀, R₂₁, R₂₂, R₂₃, R₂₄ or R₂₅independently of each other are hydrogen, COR₁₄, NO₂,

or one of R₂₁ and R₂₂, or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₄haloalkyl, C₁-C₂₀alkoxy, ═O, OR₁₅, SR₁₆, NR₁₇R₁₈,COR₁₄,

halogen, NO₂, CN, phenyl or by C₃-C₂₀cycloalkyl which is uninterruptedor is interrupted by one or more O, S, CO or NR₁₉; R₂₆ is COOR₁₅,CONR₁₇R₁₈, (CO)R₁₅; or R₂₆ has one of the meanings given for R₁₇ andR₁₈; R₂₇ is COOR₁₅, CONR₁₇R₁₈, (CO)R₁₅; or R₂₇ has one of the meaningsgiven for R₁₅; R₂₈ and R₂₉ independently of each other are hydrogen,C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₃-C₁₀cycloalkyl or phenyl, or R₂₈ and R₂₉together with N-atom to which they are attached form a 5- or 6-memberedsaturated or unsaturated ring, which is uninterrupted or interrupted byO, S or NR₁₉, and which 5- or 6-membered saturated or unsaturated ringis not condensed or to which 5- or 6-membered saturated or unsaturatedring a benzene ring is condensed; R₃₀ is hydrogen, OH, C₁-C₂₀alkyl,C₁-C₄haloalkyl, C₂-C₂₀alkyl which is interrupted by one or more O, CO orby NR₁₉, or is C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby O, S, CO or NR₁₉, or R₃₀ is phenyl, naphthyl, phenyl-C₁-C₄alkyl,OR₁₅, SR₁₆ or NR₁₇R₁₈; R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈independently of each other are hydrogen,

NO₂, COR₁₄, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₁₉; or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both,R₃₃ and R₃₄ and R₃₅ and R₃₆ are

provided that at least two oxime ester groups selected from the groupconsisting of

are present in the molecule.
 2. The compound of claim 1, wherein: R₁,R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ independently of each other arehydrogen, C₁-C₂₀alkyl,

provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄; X is CO or a direct bond; R₁₁ isC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, orM, or R₁₁ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein the interruptedC₁-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₅, SR₁₆, COOR₁₅, CONR₁₇R₁₈, NR₁₇R₁₈, or M, or R₁₁ is C₆-C₂₀aryl orC₃-C₂₀heteroaryl each of which is unsubstituted or substituted by one ormore phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₅, SR₁₆, NR₁₇R₁₈, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₁₉, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₅, CONR₁₇R₁₈,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ or NR₁₇R₁₈; R₁₂ is C₁-C₂₀alkyl,phenyl, or C₁-C₈alkoxy; R₁₃ is phenyl, naphthyl, or C₃-C₂₀heteroaryleach of which is unsubstituted or substituted by one or more phenyl,halogen, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, M, or by C₂-C₂₀alkyl whichis interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene,naphthylene or by NR₁₉, or each of which is substituted by one or moreC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₅, CONR₁₇R₁₈, phenyl, C₃-C₈cycloalkyl, C₄-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₄-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆, NR₁₇R₁₈or by M, or R₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted byone or more halogen, OR₁₅, SR₁₆, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀ heteroaryloxycarbonyl, NR₁₇R₁₈, COOR₁₅,CONR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂, phenyl or by M, or R₁₃ is C₁-C₂₀alkylwhich is substituted by phenyl which is substituted by halogen,C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆ or by NR₁₇R₁₈, or R₁₃ isC₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O),phenylene, naphthylene, or NR₁₉, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₅, COOR₁₅,CONR₁₇R₁₈, phenyl, M, or by phenyl which is substituted by OR₁₅, SR₁₆ orNR₁₇R₁₈; M is

k is an integer 1-10; m is 1 or 2; R′₁₂ has one of the meanings as givenfor R₁₂; R′₁₃ has one of the meanings as given for R₁₃; R″₁₃ isC₁-C₂₀alkyl which is unsubstituted or substituted by phenyl or by phenylwhich is substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆or by NR₁₇R₁₈, or R″₁₃ is C₂-C₂₀alkyl which is interrupted by one ormore O, CO, S, C(O)O, OC(O), phenylene, naphthylene or NR₁₉, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₅, COOR₁₅, CONR₁₇R₁₈, phenyl, or by phenyl which issubstituted by OR₁₅, SR₁₆ or NR₁₇R₁₈, or R″₁₃ is CN, CONR₁₇R₁₈, NO₂ orC₁-C₄haloalkyl; or R″₁₃ is C₆-C₂₀aryl, each of which is unsubstituted orsubstituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈, or each of which issubstituted by one or more C₁-C₂₀alkyl; X₁ is O, CO, S or a direct bond;X₃ is O, S or NR₁₉; R₁₄ is phenyl, naphthyl, or C₃-C₂₀heteroaryl each ofwhich is unsubstituted or substituted by one or more OR₁₅, SR₁₆,NR₁₇R₁₈, M or by C₂-C₂₀alkyl which is interrupted by one or more O, S,or NR₁₉, or each of which is substituted by one or more C₁-C₂₀alkylwhich is unsubstituted or substituted by one or more halogen, COOR₁₅,CONR₁₉R₂₀, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₅, SR₁₆ orNR₁₇R₁₈; or R₁₄ is

R₁₅ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OCH₂CH₂CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl), O(CO)—(C₂-C₄)alkenyl,O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl), C₃-C₂₀cycloalkyl,SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl), O(C₁-C₂₀arylene)-M, or byC₃-C₂₀cycloalkyl which is interrupted by one or more O, or R₁₅ isC₂-C₂₀alkyl which is interrupted by one or more O, S or NR₁₉; R₁₆ ismethyl substituted by COOR₁₅, or R₁₆ is phenyl unsubstituted orsubstituted by one or more C₁-C₁₂alkyl, C₁-C₁₂alkoxy, or

R₁₇ and R₁₈ independently of each other are hydrogen, phenyl,C₁-C₂₀alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy, or R₁₇ and R₁₈ togetherwith the N-atom to which they are attached form a heteroaromatic ringsystem which is uninterrupted or is interrupted by

or R₁₇ and R₁₈ together with the N-atom to which they are attached forma group

R₁₉ is hydrogen, C₁-C₂₀alkyl, or C₂-C₂₀alkyl which is interrupted by oneor more O or CO, or R₁₉ is phenyl or naphthyl both of which areunsubstituted or substituted by one or more C₁-C₂₀alkyl, halogen,C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, COR₁₄, or

R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ independently of each other is hydrogen,COR₁₄, NO₂,

or one of R₂₁ and R₂₂ or R₂₄ and R₂₅ is

or one of R₂₀, R₂₁ or R₂₂ and one of R₂₃, R₂₄ or R₂₅ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, OR₁₅, SR₁₆, NR₁₇R₁₈, COR₁₄,

NO₂, phenyl; R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently ofeach other are hydrogen,

NO₂, COR₁₄, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₅, SR₁₆, NR₁₇R₁₈, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₁₉, or R₃₃ and R₃₄ or R₃₅ and R₃₆ or both,R₃₃ and R₃₄ and R₃₅ and R₃₆ are

provided that at least two oxime ester groups are present in themolecule.
 3. The compound of claim 1, wherein: R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉ and R₁₀ independently of each other are hydrogen,

or COR₁₄, provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,R₉, and R₁₀ is

and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, and R₁₀ is COR₁₄; X is a direct bond; R₁₁ is C₁-C₂₀alkylwhich is unsubstituted or substituted by NR₁₇R₁₈, or R₁₁ is C₂-C₂₀alkylwhich is interrupted by one or more C(O)O, OC(O) or phenylene, whereinthe interrupted C₁-C₂₀alkyl is unsubstituted or substituted by NR₁₇R₁₈,or R₁₁ is phenyl or thienyl each of which is unsubstituted orsubstituted by

R₁₂ is C₁-C₂₀alkyl; R₁₃ is phenyl or thienyl each of which isunsubstituted or substituted by one or more OR₁₅, SR₁₆, NR₁₇R₁₈, or issubstituted by one or more C₁-C₂₀alkyl, or R₁₃ is C₁-C₂₀alkyl which isunsubstituted or substituted by C₃-C₈cycloalkyl, COOR₁₅

or by M; M is

R′₁₂ has one of the meanings as given for R₁₂; R′₁₃ has one of themeanings as given for R₁₃; R″₁₃ is C₁-C₂₀alkyl, phenyl or thienyl,wherein the phenyl or thienyl is unsubstituted or substituted byC₁-C₂₀alkyl; X₁ is a direct bond; X₂ is O; X₃ is NR₁₉; R₁₄ is phenyl orthienyl each of which is unsubstituted or substituted by one or moreOR₁₅, SR₁₆, NR₁₇R₁₈ or C₁-C₂₀alkyl, or R₁₄ is

R₁₅ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen or O(C₁-C₂₀arylene)-M, or R₁₅ is C₂-C₂₀alkyl which isinterrupted by one or more O, which interrupted C₂-C₂₀alkyl isunsubstituted or substituted by O—C₆-C₂₀arylene-M; R₁₆ is phenylsubstituted by

R₁₇ and R₁₈ together with the N-atom to which they are attached form agroup

R₁₉ is C₁-C₂₀alkyl; R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ independently ofeach other is hydrogen; or one of R₂₁ and R₂₂ or R₂₄ and R₂₅ is

or R₂₀ and R₂₃ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system; R₂₆ is COOR₁₅; R₂₇ isCOOR₁₅; R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ independently of eachother are hydrogen,

NO₂ or COR₁₄, or R₃₃ and R₃₄ are

provided that at least two oxime ester groups are present in themolecule.
 4. A photopolymerizable composition comprising (a) at leastone ethylenically unsaturated photopolymerizable compound; and (b) asphotoinitiator, at least one compound of claim
 1. 5. Thephotopolymerizable composition according to claim 4, wherein thecomponent (a) is a resin obtained by reaction of a saturated orunsaturated polybasic acid anhydride with a product of the reaction ofan epoxy resin and an unsaturated monocarboxylic acid.
 6. Thephotopolymerizable composition according to claim 4, further comprisingat least one of a further photoinitiator (c) and an additive (d).
 7. Thephotopolymerizable composition according to claim 6, comprising, as theadditive (d), a pigment or a mixture of pigments or a mixture of one ormore pigments with one or more dyes.
 8. The photopolymerizablecomposition according to claim 6, comprising, as the additive (d), adispersant or a mixture of dispersants.
 9. The photopolymerizablecomposition of claim 4, comprising 0.05 to 25% by weight of thephotoinitiator (b), based on a total weight of the composition.
 10. Thephotopolymerizable composition of claim 6, comprising, as the additive(d), a photosensitizer.
 11. The photopolymerizable composition of claim4, further comprising a binder polymer (e).
 12. A process for preparingthe compound of claim 1, the process comprising reacting a correspondingoxime compound with an acyl halide of formula (II) or an anhydride offormula (III):

in the presence of at least one base, wherein: Hal is a halogen, inparticular Cl, and R₁₂ is hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl,C₁-C₂₀alkoxy or C₁-C₂₀alkyl which is unsubstituted or substituted by oneor more halogen, phenyl, C₁-C₂₀alkylphenyl or CN, or R₁₂ is phenyl ornaphthyl, each of which is unsubstituted or substituted by one or moreC₁-C₆alkyl, C₁-C₄haloalkyl, halogen, CN, OR₁₅, SR₁₆, or NR₁₇R₁₈, or R₁₂is C₃-C₂₀heteroaryl, benzyloxy or phenoxy, each of which isunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyland/or halogen.
 13. A process for photopolymerizing compounds containingethylenically unsaturated double bonds, the process comprisingirradiating the composition according to claim 4 with electromagneticradiation in the range from 150 to 600 nm, or with electron beam or withX-rays, to form a polymer product.
 14. The process of claim 13, whereinthe polymer product is a component within at least one article selectedfrom the group consisting of a pigmented paint, a nonpigmented paint, apigmented varnish, a nonpigmented varnish, a powder coating, a printingink, a printing plate, an adhesive, a pressure sensitive adhesive, adental composition, a gel coat, a photoresist for electronics, an etchresist, a liquid film, a dry film, a solder resist, a resist tomanufacture color filters, a resist to generate structures in themanufacturing processes of plasma-display panels, an electroluminescencedisplay, an and LCD, an article for encapsulating electrical andelectronic components, an article for producing magnetic recordingmaterials, a micromechanical part, a waveguide, an optical switch, aplating mask, a color proofing system, a glass fibre cable coating, ascreen printing stencil, an article for producing three-dimensionalobjects by stereolithography, an image recording material forholographic recordings, a microelectronic circuit, a decolorizingmaterial, a formulation comprising microcapsules, a photoresist materialfor a UV and visible laser direct imaging system, and an article forforming dielectric layers in a sequential build-up layer of a printedcircuit board.
 15. A coated substrate which is coated on at least onesurface with the composition according to claim
 4. 16. A process forphotographic production of relief images, the process comprisingsubjecting the coated substrate according to claim 15 to imagewiseexposure and then removing unexposed portions with a developer.
 17. Acolor filter prepared by providing red, green and blue picture elementsand a black matrix, all comprising a photosensitive resin and a pigmenton a transparent substrate, and providing a transparent electrode eitheron the surface of the substrate or on the surface of the color filterlayer, wherein said photosensitive resin comprises a polyfunctionalacrylate monomer, an organic polymer binder and the compound of claim 1as a photopolymerization initiator.
 18. A process comprisingphotopolymerization of a composition comprising at least oneethylenically unsaturated photopolymerizable compound in the presence ofthe composition of claim
 1. 19. A compound of formula (IA):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are as definedin claim 1, provided that at least one group

is replaced by a group